Haloalkylmethyleneoxyphenyl-Substituted Ketoenols

ABSTRACT

The invention relates to novel compounds of the formula (I), 
     
       
         
         
             
             
         
       
     
     in which W, X, Y, Z and CKE are each as defined above, 
     to several methods and intermediates for preparation thereof and to the use thereof as pesticides and/or herbicides. 
     The invention also relates to selective herbicidal compositions which comprise firstly haloalkylmethyleneoxyphenyl-substituted ketoenols and secondly a compound which improves crop plant compatibility. 
     The present invention further relates to the enhancement of the action of crop protection compositions comprising especially haloalkylmethyleneoxyphenyl-substituted ketoenols, by the addition of ammonium or phosphonium salts and optionally penetration enhancers, to the corresponding compositions, to methods for production thereof and to the use thereof in crop protection as insecticides and/or acaricides and/or for preventing undesired plant growth.

The present invention relates to novelhaloalkylmethyleneoxyphenyl-substituted ketoenols, to several methodsfor preparation thereof and to the use thereof as pesticides and/orherbicides. The invention also provides selective herbicidalcompositions which comprise firstlyhaloalkylmethyleneoxyphenyl-substituted ketoenols and secondly acompound which improves crop plant compatibility.

The present invention further relates to the enhancement of the actionof crop protection compositions comprising especiallyhaloalkylmethyleneoxyphenyl-substituted ketoenols by the addition ofammonium or phosphonium salts and optionally penetration enhancers, tothe corresponding compositions, to methods for production thereof and tothe use thereof in crop protection as insecticides and/or acaricidesand/or for preventing undesired plant growth.

Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones have beendescribed before (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)).In addition, N-phenylpyrrolidine-2,4-diones have been synthesized by R.Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095).Biological efficacy of these compounds has not been described.

EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of similarstructure (3-arylpyrrolidine-2,4-diones), which are not, however, knownto have any herbicidal, insecticidal or acaricidal action. Knowncompounds with herbicidal, insecticidal or acaricidal action areunsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione derivatives(EP-A-355 599, EP-A-415 211 and JP-A-12-053 670) and also substitutedmonocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893 andEP-A-442 077).

Additionally known are polycyclic 3-arylpyrrolidine-2,4-dionederivatives (EP-A-442 073) and 1H-arylpyrrolidinedione derivatives(EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885,WO 95/01 971, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395,WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO98/05638, WO 98/06721, WO 98/25928, WO 99/24437, WO 99/43649, WO99/48869, WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO03/013249, WO 03/062244, WO 2004/007448, WO 2004/024 688, WO 04/065366,WO 04/080962, WO 04/111042, WO 05/044791, WO 05/044796, WO 05/048710, WO05/049569, WO 05/066125, WO 05/092897, WO 06/000355, WO 06/029799, WO06/056281, WO 06/056282, WO 06/089633, WO 07/048545, DEA 102 00505 9892,WO 07/073856, WO 07/096058, WO 07/121868, WO 07/140881, WO 08/067873. WO08/067910, WO 08/067911, WO 08/138551, WO 09/015801, WO 09/039975, WO09/049851, WO 09/115262, EP application 08170489). Also known areketal-substituted 1H-arylpyrrolidine-2,4-diones from WO 99/16748, and(spiro)-ketal-substituted N-alkoxyalkoxy-substitutedarylpyrrolidinediones from JP-A-14 205 984 and Ito M. et al.,Bioscience, Biotechnology and Biochemistry 67, 1230-1238, (2003). Theaddition of safeners to ketoenols is likewise known in principle from WO03/013249. Also known from WO 06/024411 are herbicidal compositionscomprising ketoenols.

it is known that particular substituted Δ³-dihydrofuran-2-onederivatives possess herbicidal properties (cf. DE-A-4 014 420). Thesynthesis of the tetronic acid derivatives used as starting compounds(for example3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl-Δ³-dihydrofuranone-(2))is likewise described in DE-A-4 014 420. Compounds of similar structurewith no report of insecticidal and/or acaricidal efficacy are known fromthe publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985,(8) 1567-76. 3-Aryl-Δ³-dihydrofuranone derivatives with herbicidalacaricidal and insecticidal properties are additionally known from:EPA-528 156, EP-A-647 637, WO 95/26 954, WO 96/20 196, WO 96/25 395, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05 638, WO98/06 721, WO 99/16 748, WO 98/25 928, WO 99/43 649, WO 99/48 869, WO99/55 673, WO 01/23354, WO 01/74 770, WO 01/17 972, WO 04/024 688, WO04/080 962, WO 04/111 042, WO 05/092 897, WO 06/000 355, WO 06/029 799,WO 07/048545, WO 07/073856, WO 07/096058, WO 07/121868, WO 07/140881, WO08/067911, WO 08/083950, WO 09/015801, WO 09/039975.

3-Aryl-Δ³-dihydrothiphenone derivatives are known from WO 95/26 345,96/25 395, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO01/17972, WO 01/23354, WO 01/74770, WO 03/013249, WO 04/080 962, WO04/111 042, WO 05/092897, WO 06/029799 and WO 07/096058.

Particular phenylpyrone derivatives unsubstituted in the phenyl ringhave already become known (cf. A. M. Chirazi, T. Kappe uand E. Ziegler,Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem.Ber. 91, 2849), though no possible usability as a pesticide is reportedfor these compounds. Phenylpyrene derivatives substituted in the phenylring and having herbicidal, acaricidal and insecticidal properties aredescribed in EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO97/02 243, WO 97/16 436, WO 97/19 941, WO 97/36 868, WO 98/05638, WO99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO03/013249, WO 04/080 962, WO 04/111 042, WO 05/092897, WO 06/029799 andWO 07/096058. Additionally described are isomeric pyran-3,5-diones in WO08/071405 and WO 09/074314.

Particular 5-phenyl-1,3-thiazine derivatives unsubstituted in the phenylring have already become known (cf. E. Ziegler and E. Steiner, Monatsh.95, 147 (1964), R. Ketcham, T. Kappe and E. Ziegler, J. Heterocycl.Chem. 10, 223 (1973)), though no possible application as a pesticide isreported for these compounds. 5-Phenyl-1,3-thiazine derivativessubstituted in the phenyl ring and having herbicidal, acaricidal andinsecticidal action are described in WO 94/14 785, WO 96/2 5395, WO96/35 664, WO 97/01 535, WO 97/02 243, WO 97/02 243, WO 97/36 868, WO99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO03/013249, WO 04/080 962, WO 04/111 042, WO 05/092897, WO 06/029799 andWO 07/096058.

It is known that particular substituted 2-arylcyclopentanediones possessherbicidal, insecticidal and acaricidal properties (cf., for example,U.S. Pat. Nos. 4,283,348; 4,338,122; 4,436,666; 4,526,723; 4,551,547;4,632,698; WO 96/01 798; WO 96/03 366, WO 97/14 667 and WO 98/39281, WO99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO03/062244, WO 04/080962, WO 04/111042, WO 05/092897, WO 06/029799, WO07/080066, WO 07/096058, WO 09/019005, WO 09/019015 and EP application08166352). Also known are similarly substituted compounds;3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the publicationMicklefield et al., Tetrahedron, (1992), 7519-26 and the naturalsubstance Involutin,(−)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphenyl)cyclopent-2-enonefrom the publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. Noinsecticidal or acaricidal action is described. Also known is2-(2,4,6-trimethylphenyl)-1,3-indanedione from the publication J.Economic Entomology, 66, (1973), 584 and the published specificationDE-A-2 361 084, with a report of herbicidal and acaricidal effects.

It is known that particular substituted 2-arylcyclohexanediones possessherbicidal, insecticidal and acaricidal properties (U.S. Pat. Nos.4,175,135, 4,256,657, 4,256,658, 4,256,659, 4,257,858, 4,283,348,4,303,669, 4,351,666, 4,409,153, 4,436,666, 4,526,723, 4,613,617,4,659,372, DE-A-2 813 341, and Wheeler, T. N., J. Org. Chem. 44, 4906(1979)), WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO01/74770, WO 03/013249, WO 04/080 962, WO 04/111 042, WO 05/092897, WO06/029799, WO 07/096058, WO 08/071405, WO 08/110307, WO 08/110308 and WO08/145336.

It is known that particular substituted 4-arylpyrazolidine-3,5-dionespossess acaricidal, insecticidal and herbicidal properties (cf., forexample, WO 92/16 510, EP-A-508 126, WO 96/11 574, WO 96/21 652, WO99/47525, WO 01/17 351, WO 01/17 352, WO 01/17 353, WO 01/17 972, WO01/17 973, WO 03/028 466, WO 03/062 244, WO 04/080 962, WO 04/111 042,WO 05/005428, WO 05/016873, WO 05/092897, WO 06/029799 and WO07/096058).

It is known that particular tetrahydropyridones possess herbicidalproperties (JP 0832530). Also known are specific4-hydroxytetrahydropyridones with acaricidal, insecticidal andherbicidal properties (JP 11152273). Additionally disclosed have been4-hydroxytetrahydropyridones as pesticides and herbicides in WO 01/79204and WO 07/096058.

It is known that particular 5,6-dihydropyrone derivatives, as proteaseinhibitors, have antiviral properties (WO 95/14012). Additionally knownis 4-phenyl-6-(2-phenethyl)-5,6-dihydropyrone from the synthesis ofkavalactone derivatives (Kappe et al., Arch. Pharm. 309, 558-564(1976)). Also known are 5,6-dihydropyrone derivatives as intermediates(White, J. D., Brenner, J. B., Deinsdale, M. J., J. Amer. Chem. Soc. 93,281-282 (1971)). 3-Phenyl-5,6-dihydropyrone derivatives withapplications in crop protection are described in WO 01/98288 and WO07/09658.

4-Phenyl-substituted [1,2]-oxazine-3,5-diones were described asherbicides for the first time in WO 01/17972. Additionally describedwere 4-acyl-substituted [1,2]-oxazine-3,5-diones as pesticides, but inparticular as herbicides and growth regulators, for example in EP-A-3948 89; WO 92/07837, U.S. Pat. No. 5,728,831, and as herbicides andpesticides in WO 03/048138.

The herbicidal and/or acaricidal and/or insecticidal efficacy and/orbreadth of action and/or the plant compatibility of the known compounds,especially with respect to crop plants, is, however, not alwayssatisfactory.

Novel compounds of the formula (I) have now been found

in which

-   W is hydrogen, alkyl, halogen, haloalkyl, alkoxy or haloalkoxy,-   X is alkyl, alkenyl, alkynyl, halogen, alkoxy, haloalkyl, haloalkoxy    or cyano,-   Y is hydrogen, alkyl, alkoxy or halogen,-   Z is a group

in which J¹ and J² are each independently hydrogen or halogen and J³ ishalogen or a haloalkyl group,

-   CKE is one of the groups

in which

-   U is —S—, —S(O)—, —S(O)₂—, —O—,

-    an S═N—, S(O)═N— or

-    group or is optionally Q³- and Q⁴-substituted C₁-C₄-alkylene which    may optionally be interrupted by oxygen,-   A is hydrogen, in each case optionally halogen-substituted alkyl,    alkenyl, alkoxyalkyl, alkylthioalkyl, or is saturated or    unsaturated, optionally substituted cycloalkyl in which at least one    ring atom is optionally replaced by a heteroatom, or in each case    optionally halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-,    cyano- or nitro-substituted aryl, arylalkyl or hetaryl,-   B is hydrogen, alkyl or alkoxyalkyl, or-   A and B together with the carbon atom to which they are bonded are a    saturated or unsaturated, unsubstituted or substituted cycle    optionally containing at least one heteroatom,-   D is hydrogen or an optionally substituted radical from the group of    alkyl, alkenyl, alkynyl, alkoxyalkyl, saturated or unsaturated    cycloalkyl in which one or more ring members are optionally replaced    by heteroatoms, or in each case optionally substituted arylalkyl,    aryl, hetarylalkyl or hetaryl, or-   A and D together with the atoms to which they are bonded are a    saturated or unsaturated cycle which is unsubstituted or substituted    in the A, D moiety and optionally contains at least one (in the case    of CKE=8 and 11 one further) heteroatom, or-   A and Q¹ together are in each case optionally substituted alkanediyl    or alkenediyl, which may optionally be interrupted by at least one    heteroatom,

-    or,-   B and Q² together with the atoms to which they are bonded are a    saturated or unsaturated cycle which is unsubstituted or substituted    in the B, Q² moiety and optionally contains at least one heteroatom,    or-   D and Q¹ together with the atoms to which they are bonded are a    saturated or unsaturated cycle which is unsubstituted or substituted    in the D, Q¹ moiety and optionally contains at least one heteroatom,-   Q¹ is hydrogen, alkyl, alkoxyalkyl, optionally substituted    cycloalkyl in which one methylene group is optionally replaced by    oxygen or sulphur, or is optionally substituted phenyl,-   Q², Q⁴, Q⁵ and Q⁶ are each independently hydrogen or alkyl,-   Q³ is hydrogen, in each case optionally substituted alkyl, alkoxy,    alkylthio, alkoxyalkyl, alkylthioalkyl, or is optionally substituted    cycloalkyl in which one or two methylene groups are optionally    replaced by oxygen or sulphur, or is optionally substituted phenyl,    or-   Q¹ and Q² together with the carbon atom in which they are bonded are    an unsubstituted or substituted cycle optionally containing one    heteroatom, or-   Q³ and Q⁴ together with the carbon atom to which they are bonded are    a saturated or unsaturated, unsubstituted or substituted cycle    optionally containing at least one heteroatom, or-   A and Q³ together with the carbon atom to which they are bonded are    a saturated or unsaturated, unsubstituted or substituted cycle    optionally containing at least one heteroatom, or-   A and Q⁵ together with the carbon atom to which they are bonded are    a saturated or unsaturated, unsubstituted or substituted cycle    optionally containing at least one heteroatom,-   G is hydrogen (a) or one of the groups

in which

-   -   E is one metal ion equivalent or one ammonium ion,    -   L is oxygen or sulphur.    -   M is oxygen or sulphur,    -   R¹ is in each case optionally halogen-substituted alkyl,        alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, or is        optionally halogen- alkyl- or alkoxy-substituted cycloalkyl        which may be interrupted by at least one heteroatom, or is in        each case optionally substituted phenyl, phenylalkyl, hetaryl,        phenoxyalkyl or hetaryloxyalkyl,    -   R² is in each case optionally halogen-substituted alkyl,        alkenyl, alkoxyalkyl, polyalkoxyalkyl, or in each case        optionally substituted cycloalkyl, phenyl or benzyl,    -   R³, R⁴ and R⁵ are each independently in each case optionally        halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino,        alkylthio, alkenylthio, cycloalkylthio, or in each case        optionally substituted phenyl, benzyl, phenoxy or phenylthio,

-   R⁶ and R⁷ are each independently hydrogen, in each case optionally    halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl,    optionally substituted phenyl, optionally substituted benzyl, or,    together with the nitrogen atom to which they are bonded, a cycle    optionally interrupted by oxygen or sulphur.

The compounds of the formula (I) may be present in differentcomposition, also depending on the type of substituents, as geometricand/or optical isomers or isomer mixtures, which can optionally beseparated in a customary manner. Both the pure isomers and the isomermixtures are usable in inventive compositions and their action can beenhanced by inventive ammonium or phosphonium salts. For the sake ofsimplicity, reference is always made hereinafter to compounds of theformula (I), although this means both the pure compounds and possiblyalso mixtures with different proportions of isomeric compounds.

Taking account of the meanings (1) to (11) of the CKE group, thefollowing principal structures (I-1) to (I-11) arise:

in which

A, B, D, G, Q¹, Q², Q⁵, Q⁶, U, W, X, Y and Z are each as defined above.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-1-a) to(I-1-g), arise when CKE is the group (1),

in which

A, B, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-2-a) to(I-2-g), arise when CKE is the group (2),

in which

A, B, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-3-a) to(I-3-g), arise when CKE is the group (3),

in which

A, B, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Depending on the position of the substituent G, the compounds of theformula (I-4) may be present in the two isomeric forms of the formulae(I-4-A) and (I-4-B),

which is expressed by the broken line in the formula (I-4).

The compounds of the formulae (I-4-A) and (I-4-B) may be present eitheras mixtures or in the form of pure isomers thereof. Mixtures of thecompounds of the formulae (I-4-A) and (I-4-B) can optionally beseparated in a manner known per se by physical methods, for example bychromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter. This does not rule out the possibility thatthe compounds may be present in the form of the isomer mixtures or inthe other isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-4-a) to(I-4-g), arise when CKE is the group (4),

in which

A, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-5-a) to(I-5-g), arise when CKE is the group (5),

in which

A, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Depending on the position of the substituent G, the compounds of theformula (I-6) may be present in the two isomeric forms of the formulae(I-6-A) and (I-6-B),

which is expressed by the broken line in the formula (I-6).

The compounds of the formulae (I-6-A) and (I-6-B) may be present eitheras mixtures or in the form of pure isomers thereof. Mixtures of thecompounds of the formulae (I-6-A) and (I-6B) can optionally be separatedby physical methods, for example by chromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter.

This does not rule out the possibility that the compounds may be presentin the form of the isomer mixtures or in the other isomeric form in eachcase.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-6-a) to(I-6-g), arise when CKE is the group (6),

in which

A, B, Q¹, Q², E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areeach as defined above.

Depending on the position of the substituent G, the compounds of theformula (I-7) may be present in the two isomeric forms of the formulae(I-7-A) and (I-7-B), which is expressed by the broken line in theformula (I-7):

The compounds of the formulae (I-7A) and (I-7-B) may be present eitheras mixtures or in the form of pure isomers thereof. Mixtures of thecompounds of the formulae (I-7-A) and (I-7-B) can optionally beseparated by physical methods, for example by chromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter. This does not rule out the possibility thatthe compound may be present in the form of the isomer mixtures or in theother isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-7-a) to(I-7-g), arise when CKE is the group (7),

in which

A, B, E, L, M, Q⁵, Q⁶, U, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areeach as defined above.

Depending on the position of the substituent G, the compounds of theformula (I-8) may be present in the two isomeric forms (I-8-A) and(I-8-B),

which is expressed by the broken line in the formula (I-8).

The compounds of the formulae (I-8-A) and (I-8-B) may be present eitheras mixtures or in the form of pure isomers thereof. Mixtures of thecompounds of the formulae (I-8-A) and (I-8-B) can optionally beseparated in a manner known per se by physical methods, for example bychromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter. This does not rule out the possibility thatthe compounds may be present in the form of the isomer mixtures or inthe other isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-8-a) to(I-8-g), arise when CKE is the group (8),

in which

A, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

Depending on the position of the substituent G, the compounds of theformula (I-9) may be present in the two isomeric forms of the formulae(I-9-A) and (I-9-B), which is expressed by the broken line in theformula (I-9):

The compounds of the formulae (I-9-A) and (I-9-B) may be present eitheras mixtures or in the form of pure isomers thereof. Mixtures of thecompounds of the formulae (I-9-A) and (I-9-B) can optionally beseparated in a manner known per se by physical methods, for example bychromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter. This does not rule out the possibility thatthe compounds may be present in the form of the isomer mixtures or inthe other isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-9-a) to(I-9-g), arise when CKE is the group (9),

in which

A, B, D, E, L, M, Q¹, Q², W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areeach as defined above.

Depending on the position of the substituent G, the compounds of theformula (I-10) may be present in the two isomeric forms of the formulae(I-10-A) and (I-10-B),

which is expressed by the broken line in the formula (I-10).

The compounds of the formulae (I-10-A) and (I-10-B) may be presenteither as mixtures or in the form of pure isomers thereof. Mixtures ofthe compounds of the formulae (I-10-A) and (I-10-B) can optionally beseparated in a manner known per se by physical methods, for example bychromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter, This does not rule out the possibility thatthe compounds may be present in the form of the isomer mixtures or inthe other isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-10-a) to(I-10-g), arise when CKE is the group (10),

in which

A, B, E, L, M, Q¹, Q², W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ areeach as defined above.

Depending on the position of the substituent G, the compounds of theformula (I-11) may be present in the two isomeric forms of the formulae(I-11-A) and (I-11-B), which is expressed by the broken line in theformula (I-11).

The compounds of the formulae (I-11-A) and (I-11-B) may be presenteither as mixtures or in the form of pure isomers thereof. Mixtures ofthe compounds of the formulae (I-11-A) and (I-11-B) can optionally beseparated in a manner known per se by physical methods, for example bychromatographic methods.

For reasons of better clarity, only one of the possible isomers in eachcase is shown hereinafter. This does not rule out the possibility thatthe compounds may be present in the form of the isomer mixtures or inthe other isomeric form in each case.

Taking account of the different meanings (a), (b), (c), (d), (e), (f)and (g) of the G group, the following principal structures (I-11-a) to(I-11-g), arise when CKE is the group (11),

in which

A, B, D, E, L, M, W, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each asdefined above.

It has additionally been found that the novel compounds of the formula(I) are obtained by one of the processes described hereinafter:

-   (A) Substituted 3-phenylpyrrolidine-2,4-diones or enols thereof, of    the formula (I-1-a)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above,    -   are obtained when    -   N-acylamino acid esters of the formula (II)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above, and    -   R⁸ is alkyl (preferably C₁-C₆-alkyl),    -   are intramolecularly condensed in the presence of a diluent and        in the presence of a base.

-   (B) It has also been found that substituted    3-phenyl-4-hydroxy-Δ³-dihydrofuranone derivative of the formula    (I-2-a)

in which

-   -   A, B, W, X, Y and Z are each as defined above,    -   are obtained when    -   carboxylic esters of the formula (III)

in which

-   -   A, B, W, X, Y, Z and R⁸ are each as defined above,    -   are intramolecularly condensed in the presence of a diluent and        in the presence of a base.

-   (C) It has additionally been found that substituted    3-phenyl-4-hydroxy-Δ³-dihydrothiophenone derivatives of the formula    (I-3-a)

in which

-   -   A, B, W, X, Y and Z are each as defined above,    -   are obtained when    -   β-ketocarboxylic esters of the formula (IV)

in which

-   -   A, B, W, X, Y, Z and R⁸ are each as defined above and    -   V is hydrogen, halogen, alkyl (preferably C₁C₆-alkyl) or alkoxy        (preferably C₁-C₈-alkoxy),    -   are intramolecularly cyclized, optionally in the presence of a        diluent and in the presence of an acid.

-   (D) It has additionally been found that the novel substituted    3-phenylpyrone derivatives of the formula (I-4-a)

in which

-   -   A, D, W, X, Y and Z are each as defined above,    -   are obtained when    -   carbonyl compounds of the formula (V)

in which

-   -   A and D are each as defined above,    -   or the silyl enol ethers thereof, of the formula (Va)

in which

-   -   A, D and R⁸ are each as defined above,    -   are reacted with ketenoyl halides of the formula (VI)

in which

-   -   W, X, Y and Z are each as defined above and    -   Hal is halogen (preferably chlorine or bromine),    -   optionally in the presence of a diluent and optionally in the        presence of an acid acceptor.

It has additionally been found,

-   (E) that the novel substituted phenyl-1,3-thiazine derivative of the    formula (I-5-a)

in which

-   -   A, W, X, Y and Z are each as defined above,    -   are obtained when thioamides of the formula (VII)

in which

-   -   A is as defined above,    -   are reacted with ketenoyl halides of the formula (VI)

in which

-   -   Hal, W, X, Y and Z are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid acceptor.

It has additionally been found,

-   (F) that compounds of the formula (I-6-a)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above,    -   are obtained when    -   ketocarboxylic esters of the formula (VIII)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above, and    -   R⁸ is alkyl (especially C₁-C₈-alkyl),    -   are intramolecularly cyclized, optionally in the presence of a        diluent and in the presence of a base.

It has also been found

-   (G) that compounds of the formula (I-7-a)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y and Z are each as defined above,    -   are obtained when    -   6-aryl-5-ketohexanoic esters of the formula (IX)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y and Z are each as defined above    -   and    -   R⁸ is alkyl (preferably C₁-C₆-alkyl),    -   are intramolecularly condensed in the presence of a diluent and        in the presence of a base.

-   (H) It has additionally been found that the compounds of the formula    (I-8-a)

in which

-   -   A, D, W, X, Y and Z are each as defined above,    -   are obtained when    -   compounds of the formula (X)

in which

-   -   A and D are each as defined above,    -   α) are reacted with compounds of the formula (VI)

in which

-   -   Hal, W, X, Y and Z are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid acceptor, or    -   β) are reacted with compounds of the formula (XI)

in which

-   -   W, X, Y and Z are each as defined above,    -   and U¹ is NH₂ or O—R⁸ where R⁸ is as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of a base, or    -   γ) are reacted with compounds of the formula (XII)

in which

-   -   A, D, W, X, Y, Z and R⁸ are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of a base.

It has also been found that the novel compounds of the formula (I-9-a)are obtained by one of the methods described hereinafter:

-   (I) Substituted tetrahydropyridine-2,4-diones or the enols thereof,    of the formula (I-9-a)

in which

-   -   A, B, D, Q¹, Q², W, X, Y and Z are each as defined above,    -   are obtained when    -   N-acylamino acid esters of the formula (XIII)

in which

-   -   A, B, D, Q¹, Q², W, X, Y and Z are each as defined above,    -   and    -   R⁸ is alkyl (preferably C₁-C₆-alkyl),    -   are intramolecularly condensed in the presence of a diluent and        in the presence of a base.

It has additionally been found that

-   (J) substituted 5,6-dihydropyrones of the formula (I-10-a)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above,    -   are obtained when    -   O-acylhydroxycarboxylic esters of the formula (XIV)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above,    -   and    -   R⁸ is alkyl (preferably C₁-C₆-alkyl),    -   are converted, optionally in the presence of a diluent and        optionally in the presence of a base.

It has additionally been found that the novel compounds of the formula(I-11-a) are obtained by one of the processes described hereinafter:

-   (K) Substituted oxazine-3,5-diones or the enols thereof, of the    formula (I-11-a)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above,    -   are obtained when    -   N-acylamino acid esters of the formula (XV)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above,    -   and    -   R⁸ is alkyl (preferably C₁-C₆-alkyl),    -   are intramolecularly condensed in the presence of a diluent and        in the presence of a base.

It has also been found

-   (L) that the compounds of the formulae (I-1-b) to (I-11-b) shown    above, in which A, B, D, Q¹, Q², Q⁵, Q⁶, R¹, U, W, X, Y and Z are    each as defined above are obtained when compounds of the formulae    (I-1-a) to (I-11-a) shown above, in which A, B, D, Q¹, Q², Q⁵, Q⁶,    U, W, X, Y and Z are each as defined above, are reacted in each case-   (α) with acid halides of the formula (XVI)

in which

-   -   R¹ is as defined above and    -   Hal is halogen (especially chlorine or bromine)    -   or

-   (β) with carboxylic anhydrides of the formula (XVII)

R¹—CO—O—CO—R¹  (XVII)

in which

-   -   R¹ is as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder;

-   (M) that the compounds of the formulae (I-1-c) to (I-11-c) shown    above, in which A, B, D, Q¹, Q², Q⁵, Q⁶, R², M, U, W, X, Y and Z are    each as defined above, and L is oxygen, are obtained when compounds    of the formulae (I-1-a) to (I-11-a) shown above, in which A, B, D,    Q¹, Q², Q⁵, Q⁶, U, W, X, Y and Z are each as defined above, are    reacted in each case    -   with chloroformic esters of chloroformic thio esters of the        formula (XVII)

R²-M-CO—Cl  (XVIII)

in which

-   -   R² and M are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder;

-   (N) that compounds of the formulae (I-1-c) to (I-11-c) shown above,    in which A, B, D, Q¹, Q², Q⁵, Q⁶, R², M, U, W, X, Y and Z are each    as defined above and L is sulphur are obtained when compounds of the    formulae (I-1-a) to (I-11-a) shown above, in which A, B, D, Q¹, Q²,    Q⁵, Q⁶, U, W, X, Y and Z are each as defined above are reacted in    each case    -   with chloromonothioformic esters or chlorodithioformic esters of        the formula (XIX)

in which

-   -   M and R² are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder,    -   and

-   (O) that compounds of the formulae (I-1-d) to (I-11-d) shown above,    in which A, B, D, Q¹, Q², Q⁵, Q⁶, R³, U, W, X, Y and Z are each as    defined above, are obtained when compounds of the formulae (I-1-a)    to (I-11-a) shown above, in which A, B, D, Q¹, Q², Q⁵, Q⁶, U, W, X,    Y and Z are each as defined above, are reacted in each case    -   with sulphony chlorides of the formula (XX)

R³—SO₂—Cl  (XX)

in which

-   -   R³is as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder,

-   (P) that compounds of the formulae (I-1-e) to (I-11-e) shown above,    in which A, B, D, L, Q¹, Q², Q⁵, Q⁶, R⁴, R⁵, U, W, Y and Z are each    as defined above, are obtained when compounds of the formulae    (I-1-a) to (I-11-a) shown above, in which A, B, D, Q¹, Q², Q⁵, Q⁶,    U, W, X, Y and Z are each as defined above, are reacted in each case    -   with phosphorus compounds of the formula (XXI)

in which

-   -   L, R⁴ and R⁵ are each as defined above and    -   Hal is halogen (especially chlorine or bromine),    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder,

-   (Q) that compounds of the formulae (I-1-f) to (I-11-f) shown above,    in which A, B D, E, Q¹, Q², Q⁵, Q⁶, U, W, X, Y and Z are each as    defined above, are obtained when compounds of the formulae (I-1-a)    to (I-11-a), in which A, B, D, Q¹, Q², Q⁵, Q⁶, U, W, X, Y and Z are    each as defined above, are reacted in each case    -   with metal compounds or amines of the formulae (XXII) and        (XXIII)

Me(OR¹⁰)_(t)  (XXII)

in which

-   -   Me is a mono- or divalent metal (preferably an alkali metal or        alkaline earth metal such as lithium, sodium, potassium,        magnesium or calcium), or an ammonium ion

-   -   t is the number 1 or 2 and    -   R¹⁰, R¹¹, R¹² are each independently hydrogen or alkyl        (preferably C₁-C₈-alkyl),    -   optionally in the presence of a diluent,

-   (R) that compounds of the formulae (I-1-g) to (I-11-g) shown above,    in which A, B, D, L, Q¹, Q², Q⁵, Q⁶, R⁶, R⁷, U, W, X, Y and Z are    each as defined above, are obtained when compounds of the formulae    (I-1a) to (I-11-a) shown above, in which A, B, D, Q¹, Q², Q⁵, Q⁶, U,    W, X, Y and Z are each as defined above, in each case

-   (α) are reacted with isocyanates or isothiocyanates of the formula    (XXIV)

R⁶—N═C=L  (XXIV)

in which

-   -   R⁶ and L are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of a catalyst, or

-   (β) are reacted with carbamyl chlorides or thiocarbamyl chlorides of    the formula (XXV)

in which

-   -   L, R⁶ and R⁷ are each as defined above,    -   optionally in the presence of a diluent and optionally in the        presence of an acid binder,

-   (S) that compounds of the formulae (I-1-a) to (I-11-g) shown above,    in which A, B, D, G, Q¹, Q², Q⁵, Q⁶, U, W, X, Y and Z are each as    defined above, are obtained when the bromine or iodine atom in    compounds of the formulae (I-1′) to (I-11′), in which A, B, D, G,    Q¹, Q², Q⁵, Q⁶, U, W, X and Y are each as defined above and Z′ is    preferably bromine or iodine

is exchanged with halogenated alcohols, for example trifluoroethanol ofthe formula (XXVI)

Z—OH  (XXVI)

in the presence of a solvent, in the presence of a copper salt (e.g.CU(I)I) and in the presence of a base (for example potassiumtert-butoxide, sodium hydride).

It has additionally been found that the novel compounds of the formula(I) have very good efficacy as pesticides, preferably as insecticides,acaricides and/or herbicides.

It has now also been found that, surprisingly, particularhaloalkylmethyleneoxyphenyl-substituted ketoenols, when applied togetherwith the compounds which improve crop plant compatibility describedhereinafter (safeners/antidotes), prevent damage to the crop plantsextremely efficiently and can be used particularly advantageously asbroadly active combination preparations for selective control ofundesired plants in useful plant crops, for example in cereals, but alsomaize, rape, soya and rice.

The invention also provides selective herbicidal compositions comprisingan effective content of an active ingredient combination, comprising, ascomponents,

-   (a′) at least one compound of the formula (I) in which CKE, W, X, Y    and Z are each as defined above    and-   (b′) at least one compound which improves crop plant compatibility    (safener).    -   The safeners are preferably selected from the group consisting        of:    -   S1) compounds of the formula (S1)

-   -   where the symbols and indices are each defined as follows:    -   n_(A) is a natural number from 0 to 5, preferably from 0 to 3;    -   R_(A) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or        (C₁-C₄)-haloalkyl;    -   W_(A) is an unsubstituted or substituted divalent heterocyclic        radical from the group of partially unsaturated or aromatic        five-membered heterocycles having 1 to 3 hetero ring atoms from        the group of N and O, where at least one nitrogen atom and at        mot one oxygen atom is present in the ring, preferably a radical        from the group of (W_(A) ¹) to (W_(A) ⁴),

-   -   m_(A) is 0 or 1;    -   R_(A) ² is OR_(A) ³, SR_(A) ³ or NR_(A) ³R_(A) ⁴ or a saturated        or unsaturated 3- to 7-membered heterocycle having at least one        nitrogen atom and up to 3 heteroatoms, preferably from the group        of O and S, which is attached via the nitrogen atom to the        carbonyl group in (S1) and which is unsubstituted or substituted        by radicals from the group of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and        optionally substituted phenyl, preferably a radical of the        formula OR_(A) ³, NHR_(A) ⁴ or N(CH₃)₂, in particular of the        formula OR_(A) ³;    -   R_(A) ³ is hydrogen or an unsubstituted or substituted aliphatic        hydrocarbon radical, preferably having a total of 1 to 18 carbon        atoms;    -   R_(A) ⁴ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or        substituted or unsubstituted phenyl;    -   R_(A) ⁵ is H, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,        (C₁-C₄)-alkoxy-(C₁-C₈)-alkyl, cyano or COOR_(A) ⁹ where R_(A) ⁹        is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,        (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, (C₁-C₆)-hydroxyalkyl,        (C₃-C₁₂)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl;    -   R_(A) ⁶, R_(A) ⁷, R_(A) ⁸ are identical or different and are        hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₃-C₁₂)-cycloalkyl        or substituted or unsubstituted phenyl;    -   preferably:    -   a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid        type (S1^(a)), preferably compounds such as        1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic        acid, ethyl        1-(2,4-dichlorphenyl-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate        S1-1) (“mefenpyr(-diethyl)”), and related compounds, as        described in WO-A-91/07874;    -   b) derivatives of dichlorophenylpyrazolecarboxylic acid        (S1^(b)), preferably compounds such as ethyl        1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2),        ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate        (S1-3), ethyl        1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate        (S1-4) and related compounds, as described in EP-A-333 131 and        EP-A-269 806;    -   c) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid        (S1^(c)), preferably compounds such as ethyl        1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5),        methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6)        and related compounds, as described, for example, in        EP-A-268554;    -   d) compounds of the triazolecarboxylic acid type (S1^(d)),        preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl        1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate        (S1-7), and related compounds, as described in EP-A-174 562 and        EP-A-346 620;    -   e) compounds of the 5-benzyl- or        5-phenyl-2-isoxazoline-3-carboxylic acid or the        5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (S1^(e)),        preferably compounds such as ethyl        5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or        ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related        compounds, as described in WO-A-91/08202, or        5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl        5,5-diphenyl-2-isoxazolinecarboxylate (S1-11)        (“isoxadifen-ethyl”) or n-propyl        5,5-diphenyl-2-isoxazolinecarboxylate (S1-12) or ethyl        5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13),        as described in patent application WO-A-95/07897.    -   S2) Quinoline derivatives of the formula (S2)

where the symbols and indices are each defined as follows:

-   -   R_(B) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or        (C₁-C₄)-haloalkyl;    -   n_(B) is a natural number from 0 to 5, preferably from 0 to 3;    -   R_(B) ² is OR_(B) ³, SR_(B) ³ or NR_(B) ³R_(B) ⁴ or a saturated        or unsaturated 3- to 7-membered heterocycle having at least one        nitrogen atom and up to 3 heteroatoms, preferably from the group        O and S, which is attached via the nitrogen atom to the carbonyl        group in (S2) and which is unsubstituted or substituted by        radicals from the group of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and        optionally substituted phenyl, preferably a radical of the        formula OR_(B) ³, NHR_(B) ⁴ or N(CH₃)₂, in particular of the        formula OR_(B) ³;    -   R_(B) ³ is hydrogen or an unsubstituted or substituted aliphatic        hydrocarbon radical, preferably having a total of 1 to 18 carbon        atoms;    -   R_(B) ⁴ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or        substituted or unsubstituted phenyl;    -   T_(B) is a (C₁- or C₂)-alkanediyl chain which is unsubstituted        or substituted by one or two (C₁-C₄)-alkyl radicals or by        [(C₁-C₃)-alkoxy]carbonyl;        preferably:    -   a) compounds of the 8-quinolinoxyacetic acid type (S2^(a)),        preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate        (“cloquintocet-mexyl” (S2-1), 1,3-dimethyl-but-1-yl        (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl        (5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl        (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl        (5-chloro-8-quinolinoxy)acetate (S2-5), methyl        (5-chloro-8-quinolinoxy)acetate (S2-6), allyl        (5-chloro-8-quinolinoxy)acetate (S2-7),        2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate        (S2-8), 2-oxo-prop-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9)        and related compounds, as described in EP-A-86 750, EP-A-94 349        and EP-A-191 736 or EP-A-0 392 366, and also        (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and        salts, for example its lithium, sodium, potassium, calcium,        magnesium, aluminium, iron, ammonium, quaternary ammonium,        sulphonium or phosphonium salts, as described in        WO-A-2002/34048;    -   b) compounds of the (5-chloro-8-quinolinoxy)malonic acid type        (S2^(b)), preferably compounds such as diethyl        (5-chloro-8-quinolinoxy)malonate, diallyl        (5-chloro-8-quinolinoxy)malonate, methyl ethyl        (5-chloro-8-quinolinoxy)malonate and related compounds, as        described in EP-A-0 582 198.    -   S3) Compounds of the formula (S3)

where the symbols and indices are each defined as follows:

-   -   R_(C) ¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,        (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably        dichloromethyl;    -   R_(C) ², R_(C) ³ are identical or different and are hydrogen,        (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,        (C₁-C₄)-haloalkyl, (C₂-C₄)-haloalkenyl,        (C₁-C₄)-alkylcarbamoyl-(C₁-C₄)-alkyl,        (C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl,        (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, dioxolanyl-(C₁-C₄-alkyl,        thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or        unsubstituted phenyl, or R_(C) ² and R_(C) ³ together form a        substituted or unsubstituted heterocyclic ring, preferably an        oxazolidine, thiazolidine, piperidine, morpholine,        hexahydropyrimidine or benzoxazine ring;    -   preferably:    -    active ingredients of the dichloroacetamide type which are        frequently used as pre-emergence safeners (soil-acting        safeners), such as, for example, “dichlormid”        (N,N-diallyl-2,2-dichloroacetamide) (S3-1), “R-29148”        (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer        (S3-2), “R-28725”        (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer        (S3-3), “benoxacor”        (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine)        (S3-4), “PPG-1292”        (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from        PPG Industries (S3-5), “DKA-24”        (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) from        Sagro-Chem (S3-6), “AD-67” or “MON 4660”        (3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane) from Nitrokemia        or Monsanto (S3-7), “TI-35” (1-dichloroacetylazepane) from        TRI-Chemical RT (S3-8) “diclonon” (dicyclonon) or “BAS145138” or        “LAB145138” (S3-9)        (3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane)        from BASF, “furilazole” or “MON 13900”        ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine)        (S3-10) and also its (R)-isomer (S3-11).    -   S4) N-Acylsulphonamides of the formula (S4) and salts thereof

where the symbols and indices are each defined as follows:

-   -   X_(D) is CH or N;    -   R_(D) ¹ is CO—NR_(D) ⁵R_(D) ⁶ or NHCO—R_(D) ⁷;    -   R_(D) ² is halogen, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy,        nitro, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulphonyl,        (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl;    -   R_(D) ³ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or        (C₂-C₄)-alkynyl;    -   R_(D) ⁴ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,        (C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,        cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulphinyl,        (C₁-C₄)-alkylsulphonyl, (C₁-C₄)-alkoxycarbonyl or        (C₁-C₄)-alkylcarbonyl;    -   R_(D) ⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,        (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₅-C₆)-cycloalkenyl, phenyl        or 3- or 6-membered heterocyclyl which contains v_(D)        heteroatoms from the group of nitrogen, oxygen and sulphur,        where the last seven radicals are substituted by v_(D)        substituents from the group of halogen, (C₁-C₆-alkoxy,        (C₁-C₆)-haloalkoxy, (C₁-C₂)-alkylsulphinyl,        (C₁-C₂)-alkylsulphonyl, (C₃-C₆)-cycloalkyl,        (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylcarbonyl and phenyl and, in        the case of cyclic radicals, also (C₁-C₄)-alkyl and        (C₁-C₄)-haloalkyl;    -   R_(D) ⁶ is hydrogen, (C₁-C₆-alkyl, (C₂-C₆)-alkenyl or        (C₂-C₆)-alkynyl, where the last three radicals are substituted        by v_(D) radicals from the group of halogen, hydroxy,        (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and (C₁-C₄)-alkylthio, or    -   R_(D) ⁵ and R_(D) ⁶ together with the nitrogen atom bearing them        form a pyrrolidinyl or piperidinyl radical;    -   R_(D) ⁷ is hydrogen, (C₁-C₄)-alkylamino, di-(C₁-C₄)-alkylamino,        (C₃-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where the last 2 radicals are        substituted by v_(D) substituents from the group of halogen,        (C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy and (C₁-C₄)-alkylthio and in        the case of cyclic radicals, also (C₁-C₄)-alkyl and        (C₁-C₄)-haloalkyl;    -   n_(D) is 0, 1 or 2;    -   m_(D) is 1 or 2;    -   v_(D) is 0, 1, 2 or 3;        among these, preference is given to compounds of the        N-acylsulphonamide type, for example of the formula (S4^(a))        below, which are known, for example, from WO-A-97/45016

in which

-   -   R_(D) ⁷ is (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where the 2        last-mentioned radicals are substituted by v_(D) substituents        from the group of halogen, (C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy        and (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also        (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl;    -   R_(D) ⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃.    -   m_(D) is 1 or 2;    -   v_(D) is 0, 1, 2 or 3;        and also        acylsulphamoylbenzamides, for example of the formula (S4^(b))        below, which are known, for example, from WO-A-99/16744,

-   -   for example those in which    -   R_(D) ⁵=cyclopropyl and (R_(D) ⁴)=2-OMe (“cyprosulfamide”,        S4-1),    -   R_(D) ⁵=cyclopropyl and (R_(D) ⁴)=5-Cl-2-OMe (S4-2),    -   R_(D) ⁵=ethyl and (R_(D) ⁴)=2-OMe (S4-3),    -   R_(D) ⁵=isopropyl and (R_(D) ⁴)=5-Cl-2-OMe (S4-4) and    -   R_(D) ⁵=isopropyl and (R_(D) ⁴)=2-OMe (S4-5)        and also        compounds of the N-acylsulphamoylphenylurea type of the formula        (S4^(c)), which are known, for example, from EP-A-365484.

in which

-   -   R_(D) ⁸ and R_(D) ⁹ are each independently hydrogen,        (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, (C₃-C₆)-alkenyl,        (C₃-C₆)-alkynyl,    -   R_(D) ⁴ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, CF₃,    -   m_(D) is 1 or 2;        for example

1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea,

1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea,

1-[4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl]-3-methylurea.

-   -   S5) Active ingredients from the class of the hydroxyaromatics        and aromatic-aliphatic carboxylic acid derivatives (S5), for        example

-    ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic    acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid,    4-fluorosalicyclic acid, 2-hydroxycinnamic acid,    1,2-dihydro-2-oxo-6-trifluoromethylpyridine-3-carboxamide,    2,4-dichlorocinnamic acid, as described in WO-A-2004/084631,    WO-A-2005/015994, WO-A-2005/016001.    -   S6) Active ingredients from the class of the        1,2-dihydroquinoxalin-2-ones (S6), for example

-    1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,    1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione,    1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one    hydrochloride,    1-[2-(diethylamino)ethyl]-6,7-dimethyl-3-thiophen-2-ylquinoxalin-2(1H)-one,    1-(2-methylsulphonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one,    as described in WO-A-2005/112630.    -   S7) Compounds of the formula (S7), as described in        WO-A-1998/38856.

where the symbols and indices are each defined as follows:

-   -   R_(E) ¹, R_(E) ² are each independently halogen, (C₁-C₄)-alkyl,        (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkylamino,        di-(C₁-C₄)-alkylamino nitro;    -   A_(E) is COOR_(E) ³ or COSR_(E) ⁴    -   R_(E) ³, R_(E) ⁴ are each independently hydrogen, (C₁-C₄)-alkyl,        (C₂-C₆)-alkenyl, (C₂-C₄)-alkynyl, cyanoalkyl, (C₁-C₄)-haloalkyl,        phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or        alkylammonium,    -   n_(E) ¹ is 0 or 1    -   n_(E) ², n_(E) ³ are each independently 0, 1 or 2,    -   preferably:        -   diphenylmethoxyacetic acid,        -   ethyl diphenylmethoxyacetate,        -   methyl diphenylmethoxyacetate (CAS Reg. No.: 41959-19-9)            (S7-1).    -   S8) Compounds of the formula (S8), as described in        WO-A-98/27049,

in which

-   -   X_(F) is CH or N,    -   n_(F) is, if X_(F)=N, an integer from 0 to 4 and    -    is, if X_(F)=CH, an integer from 0 to 5,    -   R_(F) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,        (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, nitro, (C₁-C₄)-alkylthio,        (C₁-C₄)-alkylsulphonyl, (C₁-C₄)-alkoxycarbonyl, optionally        substituted phenyl, optionally substituted phenoxy,    -   R_(F) ² is hydrogen or (C₁-C₄)-alkyl,    -   R_(F) ³ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₄)-alkenyl,        (C₂-C₄)-alkynyl or aryl, where each of the carbon-containing        radicals mentioned above is unsubstituted or substituted by one        or more, preferably by up to three, identical or different        radicals from the group consisting of halogen and alkoxy; or        salts thereof,    -   preferably compounds in which    -   X_(F) is CH,    -   n_(F) is an integer from 0 to 2,    -   R_(F) ¹ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,        (C₁-C₄-alkoxy, (C₁-C₄)-haloalkoxy,    -   R_(F) ² is hydrogen or (C₁-C₄)-alkyl,    -   R_(F) ³ is hydrogen, (C₁-C₈)-alkyl, (C₂-C₄)-alkenyl,        (C₂-C₄)-alkynyl or aryl, where each of the carbon-containing        radicals mentioned above is unsubstituted or substituted by one        or more, preferably by up to three, identical or different        radicals from the group consisting of halogen and alkoxy; or        salts thereof,    -   S9) Active ingredients from the class of the        3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example

-    1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone    (CAS Reg. No.: 219479-18-2),    1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone    (CAS Reg. No.: 95855-00-8), as described in WO-A-1999/000020.    -   S10) Compounds of the formula (S10^(a)) or (S10^(b))    -    as described in WO-A-2007/023719 and WO-A-2007/023764

in which

-   -   R_(G) ¹ is halogen, (C₁-C₄)-alkyl, methoxy, nitro, cyano, CF₃,        OCF₃    -   Y_(G), Z_(G) are each independently O or S,    -   n_(G) is an integer from 0 to 4,    -   R_(G) ² is (C₁-C₁₆)-alkyl, (C₂-C₆)-alkenyl, (C₃-C₆)-cycloalkyl,        aryl; benzyl, halobenzyl,    -   R_(G) ³ is hydrogen or (C₁-C₆)-alkyl.    -   S11) Active ingredients of the oxyimino compound type (S11),        which are known as seed dressings, such as, for example,    -    “oxabetrini!”        ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1),        which is known as seed dressing safener for millet against        metolachlor damage,    -    “fluoxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone        O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as        seed dressing safener for millet against metolachlor damage, and    -    “cyometrinil” or “CGA-43089”        ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is        known as seed dressing safener for millet against metolachlor        damage.    -   S12) Active ingredients from the class of the isothiochromanones        (S12), such as, for example, methyl        [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS        Reg. No.: 205121-04-6) (S12-1) and related compounds from        WO-A-1998/13361.    -   S13) One or more compounds from group (S13):    -    “naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride)        (S13-1), which is known as seed dressing safener for corn        against thiocarbamate herbicide damage,    -    “fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is        known as a safener for pretilachlor in sown rice.    -    “flurazole” (benzyl        2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3),        which is known as seed dressing safener for millet against        alachlor and metolachlor damage.    -    “CL-304415” (CAS Reg. No.: 31541-57-8)        (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4)        from American Cyanamid, which is known as a safener for corn        against imidazolinone damage,    -    “MG-191” (CAS Reg. No.: 96420-72-3)        (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from        Nitrokemia, which is known as a safener for corn,    -    “MG-838” (CAS Reg. No.: 133993-74-5) 2-propenyl        1-oxo-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from        Nitrokemia,    -    “disulfoton” (O,O-diethyl-S-2-ethylthioethyl        phosphorodithioate) (S13-7),    -    “dietholate” (O,O-diethyl-O-phenyl phosphorothioate) (S13-8),    -    “mephenate” (4-chlorophenyl methylcarbamate) (S13-9).    -   S14) Active ingredients which, in addition to a herbicidal        effect against harmful plants, also have a safener effect on        crop plants such as rice, such as, for example, “dimepiperate”        or “MY-93” (S-1-methyl-1-phenylethyl piperidine-1-carbothioate),        which is known as a safener for rice against molinate herbicide        damage,    -    “daimuron” or “SK 23”        (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as a        safener for rice against imazosulphuron herbicide damage,    -    “cumyluron”=“JC-940”        (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)-urea, see        JP-A-60087254), which is known as a safener for rice against        some herbicide damage,    -    “methoxyphenone” or “NK 049”        (3,3′-dimethyl-4-methoxybenzophenone), which is known as a        safener for rice against some herbicide damage,    -    “CSB” (1-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai,        (CAS Reg. No. 54091-06-4), which is known as a safener against        some herbicide damage in rice.    -   S15) Active ingredients, which are primarily used as herbicides,        but also have safener effect on crop plants, for example    -    (2,4-dichlorophenoxy)acetic acid (2,4-D),    -    (4-chlorophenoxy)acetic acid,    -    (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),    -    4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),

-    (4-chloro-o-tolyloxy)acetic acid (MCPA),

-    4-(4-chloro-o-tolyloxy)butyric acid,

-    4-(4-chlorophenoxy)butyric acid,

-    3,6-dichloro-2-methoxybenzoic acid (dicamba),

-    1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate    (lactidichlor-ethyl).

The most preferred compounds [components (b′)] which improve crop plantcompatibility are cloquintocet-mexyl, fenchlorazol ethyl ester,isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron, S4-1 and S4-5,particular emphasis being given to mefenpyr-diethyl. Cyprosulfamide(S4-1) is likewise emphasized.

It has now been found that, surprisingly, the above-defined activeingredient combinations of compounds of the general formula (I) andsafeners (antidotes) from group (b′) listed above, coupled with verygood useful plant compatibility, have a particularly high herbicidalefficacy and can be used in different crops, especially in cereals (inparticular wheat), but also in soya, potatoes, maize and rice, forselective weed control.

In this context, it is considered to be surprising that, from amultitude of known safeners or antidotes which are capable ofantagonizing the damaging effect of a herbicide on the crop plants,specifically the compounds of group (b′) listed above are suitable forvirtually completely eliminating the damaging effect of compounds of theformula (I) on the crop plants, without significantly impairing theherbicidal efficacy toward the weeds.

Emphasis is given here to the particularly advantageous effect of theparticularly preferred and most preferred combination partners fromgroup (b′), especially with regard to protection of cereal plants, forexample wheat, barley and rye, but also maize and rice, as crop plants.

The inventive compounds are defined in general terms by the formula (I).Preferred substituents and ranges of the radicals shown in the formulaementioned above and hereinafter are detailed as follows:

-   -   W is preferably hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy,        C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy,    -   X is preferably halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,        C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy        or cyano,    -   Y is preferably hydrogen, halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy,    -   Z is preferably a group

in which J¹ and J² are preferably each independently hydrogen, fluorineor chlorine, and J³ is preferably halogen or C₁-C₄-haloalkyl,

-   -   CKE is preferably one of the groups

-   -   U is preferably —S—, —S(O)—, —S(O)₂—, —O—,

in which n is preferably the number 0, 1 or 2,

-   -   A is preferably hydrogen or in each case optionally        halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl,        C₁-C₁₀-alkoxy-C₁-C₈-alkyl, C₁-C₁₀-alkylthio-C₁-C₆-alkyl,        optionally halogen-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted        C₃-C₈-cycloalkyl in which one or two ring members not directly        adjacent are optionally replaced by oxygen and/or sulphur, or is        in each case optionally halogen-C₁-C₆-alkyl-, C₁-C₆-haloalkyl-,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, cyano- or nitro-substituted        phenyl, naphthyl, hetaryl having 5 to 6 ring atoms (for example        furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, pyrimidyl,        thiazolyl or thienyl), phenyl-C₁-C₆-alkyl or        naphthyl-C₁-C₆-alkyl,    -   B is preferably hydrogen, C₁-C₁₂-alkyl or        C₁-C₈-alkoxy-C₁-C₆-alkyl or    -   A, B and the carbon atom to which they are bonded are preferably        saturated C₃-C₁₀-cycloalkyl or unsaturated C₅-C₁₀-cycloalkyl, in        which one ring member is optionally replaced by nitrogen, oxygen        or sulphur and which is optionally mono- or disubstituted by        C₁-C₈-alkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyloxy,        C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkoxy,        C₃-C₁₀-cycloalkyl, C₁-C₈-haloalkyl, C₂-C₆-haloalkoxy,        C₁-C₆-alkoxy-C₁-C₄-alkoxy, where the aforementioned radicals are        also possible nitrogen substituents, or    -   A, B and the carbon atom to which they are bonded are preferably        C₃-C₆-cycloalkyl which is substituted by an optionally        C₁-C₄-alkyl-substituted alkylenediyl group optionally containing        one or or two oxygen and/or sulphur atoms which are not directly        adjacent, or by an alkylenedioxyl or by an alkylenedithioyl        group, which group forms a further five-to-eight membered ring        with the carbon atom to which it is bonded, or    -   A, B and the carbon atom to which they are bonded are preferably        C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, in which two        substituents together with the carbon atoms to which they are        bonded are in each case optionally C₁-C₆-alkyl-, C₁-C₆-alkoxy-        or halogen-substituted C₂-C₆-alkanediyl, C₂-C₆-alkenediyl or        C₄-C₆-alkadienediyl in which one methylene group is optionally        replaced by oxygen or sulphur,    -   D is preferably hydrogen, in each case optionally        halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl,        C₁-C₁₀-alkoxy-C₁-C₈-alkyl, optionally halogen-, C₁-C₄-alkyl-,        C₁-C₄-alkoxy- or C₁-C₄-haloalkyl-substituted C₃-C₈-cycloalkyl,        in which one ring member is optionally replaced by oxygen or        sulphur, or in each case optionally halogen-, C₁-C₆-alkyl-,        C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkoxy-, cyano- or        nitro-substituted phenyl, hetaryl having 5 or 6 ring atoms (for        example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl,        pyrimidyl, pyrrolyl, thienyl or triazolyl), phenyl-C₁-C₆-alkyl        or hetaryl-C₁-C₆-alkyl having 5 or 6 ring atoms (for example        furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl,        pyrrolyl, thienyl or triazolyl), or    -   A and D together are preferably in each case optionally        substituted C₃-C₆-alkanediyl or C₃-C₆-alkenediyl, in which one        methylene group is optionally replaced by a carbonyl group,        oxygen or sulphur, and    -    where possible substituents in each case are:    -    halogen, hydroxyl, mercapto or in each case optionally        halogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,        C₃-C₇-cycloalkyl, phenyl or benzyloxy, or a further        C₃-C₆-alkanediyl moiety, C₃-C₆-alkenediyl moiety or a butadienyl        moiety, which is optionally substituted by C₁-C₆-alkyl or in        which two adjacent substituents with the carbon atoms to which        they are bonded optionally form a further saturated or        unsaturated cycle having 5 or 6 ring atoms (in the case of the        compound (I-1), A and D together with the atoms to which they        are bonded are then, for example, the AD-1 to AD-10 groups        further down), which may contain oxygen or sulphur, or in which        one of the following groups

-   -    is optionally present, or    -   A and Q¹ together with the carbon atoms to which they are bonded        are in each case preferably C₃-C₆-alkanediyl or C₄-C₆-alkenediyl        each optionally mono- or disubstituted identically or        differently by halogen, hydroxyl, by C₁-C₁₀-alkyl,        C₁-C₈-alkenyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃C₇ -cycloalkyl        each optionally mono- to trisubstituted identically or        differently by halogen, or by benzyloxy or phenyl each        optionally mono- to trisubstituted identically or differently by        halogen, C₁C₆-alkyl or C₁-C₆-alkoxy, and which also optionally        contains one of the following groups:

-   -    or is bridged by a C₁-C₂-alkanediyl group or by one oxygen        atom, or    -   B and Q² together are preferably optionally        C₁-C₂-alkyl-substituted C₁-C₃-alkanediyl which may optionally be        interrupted by oxygen, or    -   D and Q¹ together are preferably C₃-C₆-alkanediyl optionally        mono- or disubstituted identically or differently by        C₁-C₄-alkyl, C₁-C₄-alkoxy, or    -   Q¹ is preferably hydrogen, C₁-C₆-alkyl,        C₁-C₆-alkoxy-C₁-C₂-alkyl, optionally fluorine-, chlorine-,        C₁-C₄-alkyl-, C₁-C₂-haloalkyl- or C₁-C₄-alkoxy-substituted        C₃-C₈-cycloalkyl in which one methylene group is optionally        replaced by oxygen or sulphur, or optionally halogen-,        C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₂-haloalkyl-,        C₁-C₂-haloalkoxy-, cyano- or nitro-substituted phenyl,    -   Q², Q⁴, Q⁵ and Q⁶ are preferably each independently hydrogen or        C₁-C₄-alkyl,    -   Q³ is preferably hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₂-alkyl,        C₁-C₆-alkylthio-C₁-C₂-alkyl, optionally C₁-C₄-alkyl- or        C₁-C₄-alkoxy-substituted C₃-C₈-cycloalkyl in which one or two        methylene groups are optionally replaced by oxygen or sulphur,        or optionally halogen-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,        C₁-C₂-haloalkyl-, C₁-C₂-haloalkoxy-, cyano- or nitro-substituted        phenyl, or    -   Q¹ and Q² with the carbon atom to which they are bonded are        preferably optionally a C₁-C₆-alkyl-, C₁-C₆-alkoxy- or        C₁-C₂-haloalkyl-substituted C₃-C₇ ring in which one ring member        is optionally replaced by oxygen or sulphur,    -   Q³ and Q⁴ together with the carbon atom to which they are bonded        are preferably an optionally C₁-C₄-alkyl-, C₁-C₄-alkoxy- or        C₁-C₂-haloalkyl-substituted, saturated or unsaturated C₃-C₇ ring        in which one or two ring members are optionally replaced by        oxygen or sulphur,    -   A and Q³ together with the carbon atoms to which they are bonded        are preferably a saturated or unsaturated, optionally        C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₂-haloalkyl-substituted C₃-C₇        ring in which one or two ring members are optionally replaced by        oxygen or sulphur,    -   A and Q⁵ together with the carbon atoms to which they are bonded        are preferably a saturated or unsaturated, optionally        C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₂-haloalkyl-substituted C₃-C₇        ring in which one ring member is optionally replaced by oxygen        or sulphur,    -   G is preferably hydrogen (a) or one of the groups

-   -    especially (a), (b), (c) or (g)    -    in which        -   E is one metal ion equivalent or one ammonium ion,        -   L is oxygen or sulphur and        -   M is oxygen or sulphur,    -   R¹ is preferably in each case optionally halogen-substituted        C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl,        C₁-C₈-alkylthio-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or        optionally halogen-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted        C₃-C₈-cycloalkyl in which one or more (preferably not more than        two) ring members not directly adjacent are optionally replaced        by oxygen and/or sulphur,    -    is optionally halogen-, cyano-, nitro-, C₁-C₆-alkyl-,        C₁-C₆-alkoxy-, C₁-C₆-haloalkyl-, C₁-C₆-haloalkoxy-,        C₁-C₆-alkylthio- or C₁-C₆-alkylsulphonyl-substituted phenyl,    -    is optionally halogen-, nitro-, cyano-, C₁-C₆-alkyl-,        C₁-C₆-alkoxy-, C₁-C₆-haloalkyl- or C₁-C₆-haloalkoxy-substituted        phenyl-C₁-C₆-alkyl,    -    is optionally halogen- or C₁-C₆-alkyl-substituted 5- or        6-membered hetaryl (for example pyrazolyl, thiazolyl, pyridyl,        pyrimidyl, furanyl or thienyl),    -    is optionally halogen- or C₁-C₆-alkyl-substituted        phenoxy-C₁-C₆-alkyl, or    -    is optionally halogen-, amino- or C₁-C₆-alkyl-substituted 5- or        6-membered hetaryloxy-C₁-C₆-alkyl (for example        pyridyloxy-C₁-C₆-alkyl, pyrimidyloxy-C₁-C₆-alkyl or        thiazolyloxy-C₁-C₆-alkyl),    -   R² is in each case optionally halogen-substituted C₁-C₂₀-alkyl,        C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl,        poly-C₁-C₈-alkoxy-C₂-C₈-alkyl,    -    is optionally halogen-, C₁-C₆-alkyl- or        C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl or    -    is in each case optionally halogen-, cyano-, nitro-,        C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkyl- or        C₁-C₆-haloalkoxy-substituted phenyl or benzyl,    -   R³ is preferably optionally halogen-substituted C₁-C₈-alkyl or        in each case optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,        C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-, cyano- or nitro-substituted        phenyl or benzyl,    -   R⁴ and R⁵ are preferably each independently in each case        optionally halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy,        C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino, C₁-C₈-alkylthio,        C₂-C₈-alkenylthio, C₃-C₇-cycloalkylthio or in each case        optionally halogen-, nitro-, cyano-, C₁-C₄-alkoxy-,        C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-, C₁-C₄-haloalkylthio-,        C₁-C₄-alkyl- or C₁-C₄-haloalkyl-substituted phenyl, phenoxy or        phenylthio,    -   R⁶ and R⁷ are preferably each independently hydrogen, in each        case optionally halogen-substituted C₁-C₈-alkyl,        C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl,        C₁-C₈-alkoxy-C₁-C₈-alkyl, optionally halogen-, C₁-C₈-haloalkyl-,        C₁-C₈-alkyl- or C₁-C₈-alkoxy-substituted phenyl, optionally        halogen-, C₁-C₈-alkyl-, C₁-C₈-haloalkyl- or        C₁-C₈-alkoxy-substituted benzyl, or together are an optionally        C₁-C₄-alkyl-substituted C₃-C₆-alkylene radical in which one        carbon atom is optionally replaced by oxygen or sulphur,    -   R¹³ is preferably hydrogen, in each case optionally        halogen-substituted C₁-C₈-alkyl or C₁-C₈-alkoxy (only in the        case of the C═N—R¹³ group), optionally halogen-, C₁-C₄-alkyl- or        C₁-C₄-alkoxy-substituted C₃-C₈-cycloalkyl in which one methylene        group is optionally replaced by oxygen or sulphur, or is in each        case optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,        C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-, nitro- or cyano-substituted        phenyl, phenyl-C₁-C₄-alkyl, hetaryl-C₁-C₄-alkyl, or, only in the        case of the C═N—R¹³ group, phenyl-C₁-C₄-alkoxy or        hetaryl-C₁-C₄-alkoxy,    -   R^(14a) is preferably hydrogen or C₁-C₈-alkyl or    -   R¹³ and R^(14a) together are preferably optionally        C₁-C₄-alkyl-substituted C₄-C₆-alkanediyl which may optionally be        interrupted by oxygen or sulphur,    -   R^(15a) and R^(16a) are the same or different and are preferably        each C₁-C₆-alkyl or    -   R^(15a) and R^(16a) together are preferably a C₂-C₄-alkanediyl        radical or a C₄-alkanediyl radical which is optionally        substituted by C₁-C₆-alkyl, C₁-C₆-haloalkyl or by optionally        halogen-, C₁-C₆-alkyl-, C₁-C₄-haloalkyl-, C₁-C₆-alkoxy-,        C₁-C₄-haloalkoxy-, nitro- or cyano-substituted phenyl,    -   R^(17a) and R^(18a) are preferably each independently hydrogen,        optionally halogen-substituted C₁-C₈-alkyl or optionally        halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₄-haloalkyl-,        C₁-C₄-haloalkoxy-, nitro- or cyano-substituted phenyl or    -   R^(17a) and R^(18a) together with the carbon atom to which they        are bonded are preferably a carbonyl group or optionally        halogen-, C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted        C₅-C₇-cycloalkyl in which one methylene group is optionally        replaced by oxygen or sulphur,    -   R^(19a) and R^(20a) are preferably each independently        C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino,        C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)amino or        di-(C₃-C₁₀-alkenyl)amino.

In the radical definitions cited as preferred, halogen is fluorine,chlorine, bromine and iodine, especially fluorine, chlorine and bromine.

-   -   W is more preferably hydrogen, fluorine, chlorine, bromine,        C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy,    -   X is more preferably chlorine, bromine, iodine, C₁-C₄-alkyl,        C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl,        C₁-C₂-haloalkoxy or cyano,    -   Y is more preferably hydrogen, methyl, ethyl, fluorine,        chlorine, bromine, iodine, methoxy or ethoxy,    -   Z is more preferably the group

in which J¹ and J² are more preferably each independently hydrogen,fluorine or chlorine, and J³ is fluorine, chlorine, trichloromethyl,difluoromethyl, difluorochloromethyl, dichlorofluoromethyl ortrifluoromethyl,

-   -   CKE is more preferably one of the groups

-   -   U is more preferably —CH₂—, —CH₂—CH₂—, —O— or

-   -   A is more preferably hydrogen, in each case optionally mono- to        tri-fluorine- or -chlorine-substituted C₁-C₆-alkyl,        C₁-C₄-alkoxy-C₁-C₂-alkyl, optionally mono- to di-C₁-C₂-alkyl- or        -C₁-C₂-alkoxy-substituted C₃-C₆-cycloalkyl optionally        interrupted by one oxygen atom or (but not in the case of the        compounds of the formulae (I-3), (I-4), (I-6), (I-7), (I-9),        (I-10) and (I-11)) in each case optionally mono- to        di-fluorine-, -chlorine-, -bromine-, -C₁-C₄-alkyl-,        -C₁-C₂-haloalkyl-, -C₁-C₄-alkoxy-, -C₁-C₂-haloalkoxy, -cyano- or        -nitro-substituted phenyl, pyridyl or benzyl,    -   B is more preferably hydrogen, C₁-C₄-alkyl or        C₁-C₂-alkoxy-C₁-C₂-alkyl or    -   A, B and the carbon atom to which they are bonded are more        preferably saturated or unsaturated C₃-C₇-cycloalkyl in which        one ring member is optionally replaced by nitrogen, oxygen or        sulphur and which is optionally mono- to di-C₁-C₆-alkyl-,        -C₁-C₄-alkoxy-C₁-C₂-alkyl-, -trifluoromethyl-, -C₁-C₆-alkoxy-,        -C₃-C₆-alkenyloxy-, -trifluoroethoxy-,        -C₁-C₃-alkoxy-C₁-C₃-alkoxy- or        -C₃-C₆-cycloalkylmethoxy-substituted, where the aforementioned        radicals are also possible nitrogen substituents, with the        proviso that Q³ in that case is more preferably hydrogen or        methyl, or    -   A, B and the carbon atom to which they are bonded are more        preferably C₅-C₆-cycloalkyl which is substituted by an        optionally methyl- or ethyl-substituted alkylenediyl group        optionally containing one or two oxygen or sulphur atoms not        directly adjacent or by an alkylenedioxy group or by an        alkylenedithiol group, which group forms, with the carbon atom        to which it is bonded, a further five- or six-membered ring,        with the proviso that Q³ in that case is more preferably        hydrogen or methyl, or    -   A, B and the carbon atom to which they are bonded are more        preferably C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which two        substituents together with the carbon atoms to which they are        bonded are in each case optionally C₁-C₂-alkyl- or        C₁-C₂-alkoxy-substituted C₂-C₄-alkanediyl, C₂-C₄-alkenediyl or        butadienediyl, with the proviso that Q³ in that case is more        preferably hydrogen or methyl,    -   D is more preferably hydrogen, in each case optionally mono- to        tri-fluorine-substituted C₁-C₆-alkyl, C₃-C₆-alkenyl,        C₁-C₄-alkoxy-C₁-C₃-alkyl, in each case optionally mono- to        di-C₁-C₄-alkyl-, -C₁-C₄-alkoxy- or -C₁-C₂-haloalkyl-substituted        C₃-C₆-cycloalkyl in which one methylene group is optionally        replaced by oxygen or (only in the case of the compounds of the        formula (I-4)) is in each case optionally mono- to di-fluorine-,        -chlorine-, -bromine-, -C₁-C₄-alkyl-, -C₁-C₄-haloalkyl-,        -C₁-C₄-alkoxy- or -C₁-C₄-haloalkoxy-substituted phenyl or        pyridyl, or    -   A and D together are more preferably optionally mono- to        disubstituted C₃-C₅-alkanediyl in which one methylene group may        be replaced by a carbonyl group (but not in the case of the        compounds of the formula (I-11)), oxygen or sulphur, where        possible substituents are C₁-C₂-alkyl or C₁-C₂-alkoxy, or    -   A and D (in the case of the compounds of the formula (I-1))        together with the atoms to which they are bonded are one of the        groups AD-1 to AD-10:

or

A and D together are more preferably C₃-C₅-alkanediyl which isoptionally substituted by an optionally mono- to tetra-C₁-C₄-alkyl- or-C₁-C₃-alkoxy-C₁-C₂-alkyl-substituted alkylenedioxy group containing twooxygen atoms not directly adjacent, to form a further 5- or 6-memberedring, or

-   -   A and Q¹ are more preferably C₃-C₄-alkanediyl which is        optionally mono- or disubstituted identically or differently by        C₁-C₂-alkyl or C₁-C₂-alkoxy, and which optionally contains the        following group:

in which

-   -   R^(15a) and R^(16a) are more preferably the same or different        and are each methyl or ethyl, or    -   R^(15a) and R^(16a) together are more preferably a        C₂-C₄-alkanediyl or C₄-alkenediyl radical which is optionally        substituted by methyl or ethyl, or    -   B and Q² together are more preferably —CH₂—, —CH₂—CH₂—,        —CH₂—CH₂—CH₂—, or —CH₂—O—CH₂—, or    -   D and Q¹ together are more preferably C₃-C₄-alkanediyl, or    -   Q¹ is more preferably hydrogen, C₁-C₄-alkyl,        C₁-C₄-alkoxy-C₁-C₂-alkyl, or optionally methyl- or        methoxy-substituted C₃-C₆-cycloalkyl in which one methylene        group is optionally replaced by oxygen,    -   Q² is more preferably hydrogen, methyl or ethyl,    -   Q⁴, Q⁵ and Q⁶ are more preferably each independently hydrogen or        C₁-C₃-alkyl,    -   Q³ is more preferably hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, or        optionally mono- to di-methyl- or -methoxy-substituted        C₃-C₆-cycloalkyl optionally interrupted by one oxygen atom, or    -   Q¹ and Q² with the carbon to which they are bonded are more        preferably optionally methyl- or methoxy-substituted        C₃-C₆-cycloalkyl in which one methylene group is optionally        replaced by oxygen, with the proviso that A and B in that case        are more preferably each independently hydrogen or methyl, or    -   Q³ and Q⁴ together with the carbon to which they are bonded are        more preferably an optionally C₁-C₂-alkyl- or        C₁-C₂-alkoxy-substituted saturated C₅-C₆ ring in which one or        two ring members are optionally replaced by oxygen or sulphur,        with the proviso that A in that case is more preferably hydrogen        or methyl, or    -   A and Q³ together with the carbon to which they are bonded are        more preferably an optionally C₁-C₂-alkyl- or        C₁-C₂-alkoxy-substituted saturated C₅-C₆ ring in which one ring        member is optionally replaced by oxygen or sulphur, with the        proviso that B, Q⁴, Q⁵ and Q⁶ in that case are more preferably        each independently hydrogen or methyl, or    -   A and Q⁵ together with the carbon atoms to which they are bonded        are more preferably an optionally C₁-C₂-alkyl- or        C₁-C₂-alkoxy-substituted saturated or unsaturated C₅-C₆ ring,        with the proviso that B, Q³, Q⁴ and Q⁶ in that case are more        preferably each independently hydrogen or methyl,    -   G is more preferably hydrogen (a) or one of the groups

-   -    especially (a), (b) or (c),    -    in which        -   E is one metal ion equivalent or one ammonium ion,        -   L is oxygen or sulphur and        -   M is oxygen or sulphur,    -   R¹ is more preferably in each case optionally mono- to        tri-fluorine- or -chlorine-substituted C₁-C₈-alkyl,        C₂-C₈-alkenyl, C₁-C₄-alkoxy-C₁-C₂-alkyl,        C₁-C₄-alkylthio-C₁-C₂-alkyl or optionally mono- to di-fluorine-,        -chlorine-, -C₁-C₂-alkyl- or -C₁-C₂-alkoxy-substituted        C₃-C₆-cycloalkyl in which one or two ring members not directly        adjacent are optionally replaced by oxygen,    -    is optionally mono- to di-fluorine-, -chlorine-, -bromine-,        -cyano-, -nitro-, -C₁-C₄-alkyl-, -C₁-C₄-alkoxy-,        -C₁-C₂-haloalkyl- or -C₁-C₂-haloalkoxy-substituted phenyl,    -   R² is more preferably in each case optionally mono- to        tri-fluorine-substituted C₁-C₈-alkyl, C₂-C₈-alkenyl or        C₁-C₄-alkoxy-C₂-C₄-alkyl,    -    is optionally mono-C₁-C₂-alkyl- or -C₁-C₂-alkoxy-substituted        C₃-C₆-cycloalkyl or    -    is in each case optionally mono- to di-fluorine-, -chlorine-,        -bromine-, -cyano-, -nitro-, -C₁-C₄-alkyl-, -C₁-C₃-alkoxy-,        -trifluoromethyl- or -trifluoromethoxy-substituted phenyl or        benzyl,    -   R³ is more preferably optionally mono- to        tri-fluorine-substituted C₁-C₆-alkyl or optionally        mono-fluorine-, -chlorine-, -bromine-, -C₁-C₄-alkyl-,        -C₁-C₄-alkoxy-, -trifluoromethyl-, -trifluoromethoxy-, -cyano-        or -nitro-substituted phenyl,    -   R⁴ is more preferably C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio,        C₃-C₄-alkenylthio, C₃-C₆-cycloalkylthio, or in each case        optionally mono- fluorine-, -chlorine-, -bromine-, -nitro-,        -cyano-, -C₁-C₃-alkoxy, -C₁-C₃-haloalkoxy-, -C₁-C₃-alkylthio-,        -C₁-C₃-haloalkylthio-, -C₁-C₃-alkyl- or        -trifluoromethyl-substituted phenyl, phenoxy or phenylthio,    -   R⁵ is more preferably C₁-C₆-alkoxy or C₁-C₆-alkylthio,    -   R⁶ is more preferably C₁-C₆-alkyl, C₃-C₆-cycloalkyl,        C₁-C₆-alkoxy, C₃-C₆-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl,        optionally mono-fluorine-, -chlorine-, -bromine-,        -trifluoromethyl-, -C₁-C₄-alkyl- or -C₁-C₄-alkoxy-substituted        phenyl, optionally mono- fluorine-, -chlorine-, -bromine-,        -C₁-C₄-alkyl-, -trifluoromethyl- or -C₁-C₄-alkoxy-substituted        benzyl,    -   R⁷ is more preferably C₁-C₆-alkyl, C₃-C₆-alkenyl or        C₁-C₆-alkoxy-C₁-C₄-alkyl,    -   R⁶ and R⁷ together are more preferably an optionally methyl- or        ethyl-substituted C₄-C₅-alkylene radical in which one methylene        group is optionally replaced by oxygen or sulphur.

In the radical definitions cited as particularly preferred, halogen isfluorine, chlorine and bromine, especially fluorine and chlorine.

-   -   W is even more preferably hydrogen, chlorine, methyl or ethyl,    -   X is even more preferably chlorine, methyl, ethyl, methoxy or        ethoxy,    -   Y is even more preferably hydrogen, methyl or chlorine,    -   Z is even more preferably the group

in which J¹ and J² are even more preferably each independently hydrogenor fluorine and J³ is fluorine, chlorine or trifluoromethyl,

-   -   CKE is even more preferably one of the groups

-   -   U is even more preferably —CH₂—, —CH₂—CH₂—, —O— or

-   -   A is even more preferably hydrogen, in each case optionally        mono- to tri-fluorine-substituted C₁-C₄-alkyl or        C₁-C₂-alkoxy-C₁-C₂-alkyl, or is cyclopropyl, cyclopentyl or        cyclohexyl, and in the case of the compounds of the formula        (I-5) is optionally mono- to di-fluorine-, -chlorine-,        -bromine-, -methyl-, -ethyl-, -n-propyl-, -isopropyl-,        -methoxy-, -ethoxy-, -trifluoromethyl-, -trifluoromethoxy-,        -cyano- or -nitro-substituted phenyl,    -   B is even more preferably hydrogen, methyl or ethyl, or    -   A, B and the carbon atom to which they are bonded are even more        preferably saturated C₅-C₆-cycloalkyl in which one ring member        is optionally replaced by nitrogen, oxygen or sulphur and which        is optionally mono- or di-methyl-, -ethyl-, -methoxymethyl-,        -ethoxymethyl-, -methoxyethyl-, -ethoxyethyl-,        -trifluoromethyl-, -methoxy-, -ethoxy-, -propoxy-, -butoxy-,        -methoxyethoxy-, -ethoxyethoxy-, -allyloxy-, -trifluoroethoxy-        or -cyclopropylmethoxy-substituted, where the aforementioned        radicals are also possible nitrogen substituents, with the        proviso that Q³ in that case is even more preferably hydrogen,        or    -   A, B and the carbon atom to which they are bonded are even more        preferably C₆-cycloalkyl which is optionally substituted by an        alkylidenediyl group optionally interrupted by one oxygen atom        or by an alkylenedioxy group optionally containing two oxygen        atoms not directly adjacent, to form a further 5- or 6-membered        ring (which may be mono- or di-methyl-substituted), with the        proviso that Q³ in that case is even more preferably hydrogen,        or    -   A, B and the carbon atom to which they are bonded are even more        preferably C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl, in which two        substituents together with the carbon atoms to which they are        bonded are C₂-C₄-alkanediyl or C₂-C₄-alkenediyl or        butadienediyl, with the proviso that Q³ in that case is even        more preferably hydrogen,    -   D is even more preferably hydrogen, in each case optionally        mono- to tri-fluorine-substituted C₁-C₄-alkyl, C₃-C₄-alkenyl,        C₁-C₄-alkoxy-C₁-C₃-alkyl, or is cyclopropyl, cyclopentyl or        cyclohexyl, or (in the case of the compounds of the formula        (I-4)) is in each case optionally mono-fluorine-, -chlorine-,        -methyl-, -ethyl-, -n-propyl-, -isopropyl-, -methoxy-, -ethoxy-        or -trifluoromethyl-substituted phenyl or pyridyl,        or    -   A and D together are even more preferably optionally        mono-methyl- or -methoxy-substituted C₃-C₅-alkanediyl in which        one carbon atom is optionally replaced by a carbonyl group (but        not in the case of the compound of the formula (I-11)), oxygen        or sulphur, or is the AD-1 group, or

A and D together are even more preferably C₃-C₅-alkanediyl which isoptionally substituted by an optionally mono- todi-C₁-C₂-alkyl-substituted alkylenedioxy group containing two oxygenatoms not directly adjacent, to form a further 5-membered ring, or

-   -   A and Q¹ together are even more preferably optionally mono- or        di-methyl- or -methoxy-substituted C₃-C₄-alkanediyl which        optionally contains the following group:

-   -    in which R^(15a) and R^(16a) together are even more preferably        a C₂-C₄-alkanediyl or C₄-alkenediyl radical, or    -   B and Q² together are even more preferably —CH₂—CH₂—CH₂—, or        —CH₂—O—CH₂—, or    -   D and Q¹ together are even more preferably C₃-C₄-alkanediyl, or    -   Q¹ is even more preferably hydrogen, methyl, ethyl, propyl,        isopropyl, cyclopropyl, cyclopentyl or cyclohexyl,    -   Q² is even more preferably hydrogen, methyl or ethyl,    -   Q⁴, Q⁵ and Q⁶ are even more preferably each independently        hydrogen or methyl,    -   Q³ is even more preferably hydrogen, methyl, ethyl, propyl,        methoxy or ethoxy, or optionally mono-methyl- or        -methoxy-substituted C₃-C₆-cycloalkyl optionally interrupted by        one oxygen atom, or    -   Q¹ and Q² with the carbon atom to which they are bonded are even        more preferably optionally methyl- or methoxy-substituted        C₅-C₆-cycloalkyl in which one methylene group is optionally        replaced by oxygen, with the proviso that A and B are each        hydrogen, or    -   Q³ and Q⁴ together with the carbon to which they are bonded are        even more preferably an optionally mono-methyl- or        -methoxy-substituted, saturated C₅-C₆ ring optionally        interrupted by one oxygen atom, with the proviso that A, B, Q⁵        and Q⁶ in that case are even more preferably hydrogen,    -   G is even more preferably hydrogen (a) or one of the groups

-   -    in which        -   L is oxygen or sulphur,        -   M is oxygen or sulphur and        -   E is one metal ion equivalent or one ammonium ion,    -   R¹ is even more preferably in each case optionally        mono-chlorine-substituted C₁-C₆-alkyl, C₂-C₆-alkenyl,        C₁-C₂-alkoxy-C₁-alkyl, C₁-C₂-alkylthio-C₁alkyl, or in each case        optionally mono-fluorine, -chlorine, -methyl- or        -methoxy-substituted cyclopropyl or cyclohexyl,    -    optionally mono-fluorine-, -chlorine-, -bromine-, -cyano-,        -nitro-, -methyl-, -methoxy-, -trifluoromethyl- or        -trifluoromethoxy-substituted phenyl,    -   R² is even more preferably in each case optionally        mono-fluorine-substituted C₁-C₈-alkyl, C₂-C₆-alkenyl or        C₁-C₄-alkoxy-C₂-C₃-alkyl, phenyl or benzyl,    -   R³ is even more preferably C₁-C₈-alkyl,    -   W is especially preferably hydrogen, methyl or ethyl,    -   X is especially preferably chlorine, methyl or ethyl,    -   Y is especially preferably hydrogen,    -   Z is especially preferably OCH₂—CF₃ in the 3 position,    -   Z is especially preferably also OCH₂—CF₃in the 4 position,    -   Z is especially preferably likewise OCH₂—CF₃ in the 5 position,    -   CKE is especially preferably one of the groups

-   -   A is especially preferably methyl or ethyl,    -   B is especially preferably hydrogen or methyl,    -   A, B and the carbon atom to which they are bonded are especially        preferably saturated C₅-C₆-cycloalkyl in which one ring member        is optionally replaced by oxygen and which is optionally mono-        or di-methyl-, -ethyl-, -methoxymethyl-, -methoxy-, -ethoxy-,        -propoxy-, -butoxy-, -trifluoroethoxy-substituted, or    -   A, B and the carbon atom to which they are bonded are especially        preferably C₆-cycloalkyl which is optionally substituted by an        alkylenedioxy group containing two oxygen atoms not directly        adjacent, to form a further 5- or 6-membered ring which may be        mono- or di-methyl-substituted,    -   D is especially preferably hydrogen, or    -   A and D together are especially preferably C₃-C₅-alkanediyl in        which one carbon atom is optionally replaced by oxygen, or

A and D together are especially preferably C₃-C₅-alkanediyl which isoptionally substituted by an optionally mono- to di-methyl-substitutedalkylenedioxy group optionally containing two oxygen atoms not directlyadjacent, to form a further 5-membered ring (with emphasis, A and Dtogether are C₃-C₅-alkanediyl which is optionally substituted by analkylenedioxy group containing two oxygen atoms not directly adjacent,to form a further 5-membered ring), or

-   -   A and Q¹ together are especially preferably C₃-C₄-alkanediyl,    -   Q² is especially preferably hydrogen,    -   G is especially preferably hydrogen (a) or one of the groups

-   -    in which        -   L is oxygen,        -   M is oxygen,        -   R¹ is especially preferably C₁-C₆-alkyl,        -   R² is especially preferably C₁-C₆-alkyl.

The radical definitions and illustrations generalized above or listed inpreferred ranges can be combined as desired with one another, i.e.including between the particular ranges and preferred ranges. They applycorrespondingly to the end products, and to the precursors andintermediates.

Preference is given in accordance with the invention to the compounds ofthe formula (I) in which there is a combination of the definitionslisted above as preferred (preferably).

Particular preference is given in accordance with the invention to thecompounds of the formula (I) in which there is a combination of thedefinitions listed above as particularly preferred.

Very particular preference is given in accordance with the invention tothe compounds of the formula (I) in which there is a combination of thedefinitions listed above as even more preferred.

Special preference is given in accordance with the invention to thecompounds of the formula (I) in which there is a combination of thedefinitions listed above as especially preferred.

Emphasis is given to compounds of the formula (I) in which G ishydrogen.

Saturated or unsaturated hydrocarbon radicals such as alkyl, alkanediylor alkenyl may, also in conjunction with heteroatoms, for example inalkoxy, as far as possible, each be straight-chain or branched.

Optionally substituted radicals may, unless stated otherwise, besubstituted once or more than once, and the substituents in the case ofpolysubstitutions may be the same or different.

Apart from the compounds cited in the examples, specific mention shouldbe made of the following compounds where Z=OCH₂—CF₃:

TABLE 1 X W Y Z CH₃ H H 4 CH₃ H H 5 Cl H H 4 Cl H H 5 OCH₃ H H 4 OCH₃ HH 5 C₂H₅ H H 4 C₂H₅ H H 5 CH₃ CH₃ H 4 CH₃ CH₃ H 5 C₂H₅ CH₃ H 4 C₂H₅ C₂H₅H 4 CH₃ Cl H 4 C₂H₅ Cl H 4

Useful inventive active ingredients are especially preferably compoundsof the radical combinations for W, X, Y and Z specified in Table 1 withthe radical combinations for A, B and D cited in Tables 2a and 2b.

TABLE 2a A B D CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H C₄H₉ H H i-C₄H₉ H Hs-C₄H₉ H H t-C₄H₉ H H CH₃ CH₃ H C₂H₅ CH₃ H C₃H₇ CH₃ H i-C₃H₇ CH₃ H C₄H₉CH₃ H i-C₄H₉ CH₃ H s-C₄H₉ CH₃ H t-C₄H₉ CH₃ H C₂H₅ C₂H₅ H C₃H₇ C₃H₇ H

CH₃ H

CH₃ H

CH₃ H H₃CO—CH₂— CH₃ H H₅C₂O—CH₂— CH₃ H H₃CO—(CH₂)₂— CH₃ H H₅C₂O—(CH₂)₂—CH₃ H

CH₃ H

CH₃ H —(CH₂)₂— H —(CH₂)₄— H —(CH₂)₅— H —(CH₂)₆— H —(CH₂)₇— H

H

H —(CH₂)₂—O—(CH₂)₂— H —CH₂—O—(CH₂)₃— H —(CH₂)₂—S—(CH₂)₂— H—CH₂—CHCH₃—(CH₂)₃— H —CH₂—CHOCH₃—(CH₂)₂— H —CH₂—CHOC₂H₅—(CH₂)₂— H—CH₂—CHOC₃H₇—(CH₂)₂— H —CH₂—CHOC₄H₉—(CH₂)₂— H —CH₂—CHO(CH₂)₂OCH₃—(CH₂)₂—H

H —CH₂—CHOCH₃—(CH₂)₃— H —CH₂—CHOC₂H₅—(CH₂)₃— H —CH₂—CHOC₃H₇—(CH₂)₃— H—CH₂—CHOC₄H₉—(CH₂)₃— H —CH₂—CHO(CH₂)₂OCH₃—(CH₂)₃— H

H —(CH₂)₂—CHCH₃—(CH₂)₂— H —(CH₂)₂—CHC₂H₅—(CH₂)₂— H—(CH₂)₂—CHC₃H₇—(CH₂)₂— H —(CH₂)₂—CHi—C₃H₇—(CH₂)₂— H—(CH₂)₂—CHOCH₃—(CH₂)₂— H —(CH₂)₂—CHOC₂H₅—(CH₂)₂— H—(CH₂)₂—CHOC₃H₇—(CH₂)₂— H —(CH₂)₂—CHO—CH₂CF₃—(CH₂)₂— H—(CH₂)₂—C(CH₃)₂—(CH₂)₂— H —CH₂—(CHCH₃)₂—(CH₂)₂— H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

TABLE 2b A D B —(CH₂)₃— H —(CH₂)₄— H —CH₂—CHCH₃—CH₂— H —CH₂—CH₂—CHCH₃— H—CH₂—CHCH₃—CHCH₃— H —CH₂—CH(OCH₃)CH₂— H —CH₂—CH═CH—CH₂— H

H —CH₂—S—CH₂— H —CH₂—S—(CH₂)₂— H —(CH₂)₂—S—CH₂— H

H H CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H

H H

H H

H CH₃ CH₃ H CH₃ C₂H₅ H CH₃ C₃H₇ H CH₃ i-C₃H₇ H CH₃

H CH₃

H CH₃

H C₂H₅ CH₃ H C₂H₅ C₂H₅ H H H₃CO—(CH₂)₂— H H H₅C₂O—(CH₂)₂— H HH₃CO—CH₂—CH(CH₃)— H H H₃CO—CHCH₃—CH₂ — H CH₃ H₃CO—(CH₂)₂— H CH₃H₅C₂O—(CH₂)₂— H CH₃ H₃CO—CH₂—CH(CH₃)— H CH₃ H₃CO—CHCH₃—CH₂— H

Active ingredients emphasized are especially preferred compounds withthe radical combinations for W, X, Y and Z specified in Table 1 and theradical combinations specified for A, B and D in Tables 2a and 2b.

Useful inventive active ingredients additionally especially preferablyinclude compounds of radical combinations for W, X, Y and Z specified inTable 1 with the radical combinations for A and B specified in Table 3.

TABLE 3 A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉H CH₃ CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃t-C₄H₉ CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ H₃CO—CH₂— CH₃ H₅C₂O—CH₂— CH₃ H₃CO—(CH₂)₂— CH₃ H₅C₂O—(CH₂)₂—

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇—

—(CH₂)₂—O—(CH₂)₂— —CH₂—O—(CH₂)₃— —(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃——CH₂—CHOCH₃—(CH₂)₃— —CH₂—CHOC₂H₅—CH₂—(CH₂)₃— —CH₂—CHOC₃H₇—(CH₂)₃——CH₂—CHOC₄H₉—(CH₂)₃— —CH₂—CHO(CH₂)₂OCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi-C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHO—CH₂CF₃—(CH₂)₂— —(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

Active ingredients emphasized are especially preferably compounds withthe radical combinations for W, X, Y and Z specified in Table 1 and theradical combinations specified for A and B in Table 3.

In the literature it has already been described how the action ofvarious active ingredients can be boosted by addition of ammonium salts.The salts in question, however, are detersive salts (for example WO95/017817) or salts which have relatively long alkyl substituents and/oraryl substituents and which have a permeabilizing action or whichincrease the active ingredient's solubility (for example EP-A 0 453 086,EP-A 0 664 081, FR-A 2 600 494, U.S. Pat. No. 4,844,734, U.S. Pat. No.5,462,912, U.S. Pat. No. 5,538,937, US-A 03/0223949, US-A 05/0009880,US-A 05/0096386). Moreover, the prior art describes the action only forparticular active ingredients and/or particular applications of thecorresponding compositions. In other cases, in turn, the salts inquestion are those of sulphonic acids, where the acids themselves have aparalytic action on insects (U.S. Pat. No. 2,842,476). A boost to actionby ammonium sulphate, for example, is described by way of example, forthe herbicides glyphosate, phosphinothricin and for phenyl-substitutedcyclic ketoenols (U.S. Pat. No. 6,645,914, EP-A2 0 036 106, WO07/068427). A corresponding boost to action in the case of insecticideshas already been described by WO 07/068428.

The use of ammonium sulphate as a formulating assistant has also beendescribed for certain active ingredients and applications (WO 92/16108),but its purpose therein is to stabilize the formulation, not to boostthe action.

It has been found, likewise surprisingly, that the action ofinsecticides and/or acaricides and/or herbicides from the class of thehaloalkylmethyleneoxyphenol-substituted ketoenols of the formula (I) canbe boosted significantly through the addition of ammonium salts orphosphonium salts to the application solution or through theincorporation of these salts into a formulation comprising thehaloalkylmethyleneoxyphenyl-substituted ketoenols of the formula (I).The present invention therefore provides for the use of ammonium saltsor phosphonium salts for boosting the action of crop protectioncompositions which comprise as their active ingredient herbicidal and/orinsecticidal and/or acaricidal haloalkylmethyleneoxyphenyl-substitutedketoenols of the formula (I). The invention likewise providescompositions which comprise herbicidal and/or acaricidal and/orinsecticidal haloalkylmethyleneoxyphenyl-substituted ketoenols of theformula (I) and action-boosting ammonium salts or phosphonium salts,including not only formulated active ingredients but also ready-to-usecompositions (spray liquors). The invention further provides, finally,for the use of these compositions for controlling insect pests and/orspider mites and/or unwanted plant growth.

The compounds of the formula (I) possess a broad insecticidal and/oracaricidal and/or herbicidal activity, but in specific cases theactivity and/or plant tolerance leaves something to be desired.

The active ingredients can be used in the compositions according to theinvention in a broad concentration range. The concentration of theactive ingredients in the formulation is typically 0.1%-50% by weight.

Formula (III′) provides a definition of the ammonium salts andphsophonium salts which, according to the invention, boost the activityof crop protection compositions comprising fatty acid biosynthaseinhibitors

in which

-   -   D is nitrogen or phosphorus,    -   D is preferably nitrogen,    -   R²⁶, R²⁷, R²⁸ and R²⁹ independently of one another represent        hydrogen or in each case optionally substituted C₁-C₈-alkyl or        mono- or polyunsaturated, optionally substituted C₁-C₈-alkylene,        the substituents being selectable from halogen, nitro and cyano,    -   R²⁶, R²⁷, R²⁸ and R²⁹ independently of one another preferably        represent hydrogen or in each case optionally substituted        C₁-C₄-alkyl, the substituents being selectable from halogen,        nitro and cyano,    -   R²⁶, R²⁷, R²⁸ and R²⁹ independently of one anther particularly        preferable represent hydrogen, methyl, ethyl, n-propyl,        isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl,    -   R²⁶, R²⁷, R²⁸ and R²⁹ very particularly preferably represent        hydrogen,    -   n is 1, 2, 3 or 4,    -   n is preferably 1 or 2,    -   R³⁰ is an organic or inorganic anion,    -   R³⁰ is preferably hydrogencarbonate, tetraborate, fluoride,        bromide, iodide, chloride, monohydrogenphosphate,        dihydrogenphosphate, hydrogensulphate, tartrate, sulphate,        nitrate, thiosulphate, thiocyanate, formate, lactate, acetate,        propionate, butyrate, pentanoate or oxalate,    -   R³⁰ is more preferably lactate, sulphate, nitrate, thiosulphate,        thiocyanate, oxalate or formate,    -   R³⁰ is most preferably sulphate.

Combinations emphasized in accordance with the invention of activeingredient, salt and penetration enhancer are listed in the table below.“Penetration enhancer as per test” means here that any compound thatacts as a penetration enhancer in the cuticle penetration test (Baur etal., 1997, Pesticide Science 51, 131-152) is suitable.

The ammonium salts and phosphonium salts of the formula (III′) can beused in a broad concentration range to boost the activity of cropprotection compositions comprising ketoenols. In general the ammoniumsalts or phosphonium salts are used in the ready-to-use crop protectioncomposition in a concentration of 0.5 to 80 mmol/l, preferably 0.75 to37.5 mmol/l, more preferably 1.5 to 25 mmol/l. In the case of aformulated product the ammonium salt and/or phosphonium saltconcentration in the formulation is chosen such that it is within thesestated general, preferred or particularly preferred ranges after theformulation has been diluted to the desired active ingredientconcentration. The concentration of the salt in the formulation istypically 1%-50% by weight.

In one preferred embodiment of the invention the activity is boosted byadding to the crop protection compositions not only an ammonium saltand/or phosphonium salt but also, additionally, a penetration enhancer.It is considered entirely surprising that even in these cases an evengreater boost to activity is observed. The present invention thereforelikewise provides for the use of a combination of penetration enhancerand ammonium salts and/or phosphonium salts to boost the activity ofcrop protection compositions which comprise insecticidal and/oracaricidal and/or herbicidal haloalkylmethyleneoxyphenyl-substitutedketoenols of the formula (I) as active ingredient. The inventionlikewise provides compositions which comprise herbicidal and/oracaricidal and/or insecticidal haloalkylmethyleneoxyphenyl-substitutedketoenols of the formula (I), penetration enhancers and ammonium saltsand/or phosphonium salts, including specifically not only formulatedactive ingredients but also ready-to-use compositions (spray liquors).The invention additionally provides, finally, for the use of thesecompositions for controlling harmful insects and/or spider mites and/orundesired plant growth.

In the present context, suitable penetration enhancers are all thosesubstances which are usually employed to improve penetration ofagrochemically active ingredients into plants. In this context,penetration enhancers are defined in that they penetrate from theaqueous spray liquor and/or the spray coating into the cuticles of theplant, thus increasing the mobility of active ingredients in thecuticles. The method described in the literature (Baur et al, 1997,Pesticide Sciences 51, 131-152) can be used for determining thisproperty.

Examples of useful penetration enhancers include alkanol alkoxylates.Penetration enhancers of the invention are alkanol alkoxylates of theformula (IV′)

R—O-(-AO)_(v)—R′  (IV)

in which

-   -   R is straight-chain or branched alkyl having 4 to 20 carbon        atoms,    -   R′ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,        isobutyl, tert-butyl, n-pentyl or n-hexyl,    -   AO is an ethylene oxide radical, a propylene oxide radical, a        butylene oxide radical or is mixtures of ethylene oxide and        propylene oxide radicals or butylene oxide radicals, and    -   v is a number from 2 to 30

One preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

R—O-(-EO—)_(n)—R′  (IV′-a)

in which

-   -   R is as defined above,    -   R′ is as defined above,    -   EO is —CH₂—CH₂—O—, and    -   n is a number from 2 to 20.

A further preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

R—O—(-EO—)_(p)—(—PO—)_(q)—R′  (IV′-b)

in which

-   -   R is as defined above,    -   R′ is as defined above,    -   EO is —CH₂—CH₂—O—.    -   PO is

-   -   p is a number from 1 to 10, and    -   q is a number from 1 to 10.

A further preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

R—O—(—PO—)_(r)-(EO—)_(s)—R′  (IV′-c)

in which

-   R is as defined above,-   R′ is as defined above.    -   EO is —CH₂—CH₂—O—,    -   PO is

-   -   r is a number from 1 to 10, and    -   s is a number from 1 to 10.

A further preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

R—O—(-EO—)_(p)—(—BO—)_(q)—R′  (IV′-d)

in which

-   -   R and R′ are as defined above,    -   EO is —CH₂—CH₂—O—,    -   BO is

-   -   p is a number from 1 to 10 and    -   q is a number from 1 to 10.

A further preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

R—O—(—BO—)_(r)—(-EO—)_(s)—R′  (IV′-e)

in which

-   -   R and R′ are as defined above,

BO is

-   -   EO is —CH₂—CH₂—O—,    -   r is a number from 1 to 10 and    -   s is a number from 1 to 10.

A further preferred group of penetration enhancers is that of alkanolalkoxylates of the formula

CH₃—(CH₂)_(t)—CH₂—O—(—CH₂—CH₂—O—)_(u)—R′  (IV′-f)

in which

-   -   R′ is as defined above,    -   t is a number from 8 to 13.    -   u is a number from 6 to 17.

In the formulae indicated above,

-   -   R is preferably butyl, isobutyl, n-pentyl, isopentyl, neopentyl,        n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl,        isononyl, decyl, n-dodecyl, isododecyl, lauryl, myristyl,        isotridecyl, trimethylnonyl, palmityl, stearyl or eicosyl.

One example of an alkanol alkoxylate of the formula (IV-c) is2-ethylhexyl alkoxylate of the formula

in which

-   -   EO is —CH₂—CH₂—O—,    -   PO is

-   -    and    -   the numbers 8 and 6 represent average values.

One example of an alkanol alkoxylate of the formula (IV-d) is theformula

CH₃—(CH₂)₁₀—O—(-EO—)₆(—BO—)₂—CH₃  (IV′-d-1)

in which

-   -   EO is —CH₂—CH₂—O—,    -   BO is

-   -    and    -   the numbers 10, 6, and 2 represent average values.

Particularly preferred alkanol alkoxylates of the formula (IV′-f) arecompounds of this formula in which

-   t is a number from 9 to 12 and-   u is a number from 7 to 9.

A very particular preferred alkanol alkoxylate is that of the formula(IV′-f-1)

CH₃—(CH₂)_(t)—CH₂—O—(—CH₂—CH₂—O—)_(u)—H  (IV′-f-1)

in which

-   -   t is the average value 10.5 and    -   u is the average value 8.4.

A general definition of the alkanol alkoxylates is given by the formulaeabove. These substances are mixtures of compounds of the stated typewith different chain lengths. The indices therefore have average valueswhich may also deviate from whole numbers.

The alkanol alkoxylates of the formulae stated are known and in somecases are available commercially or can be prepared by known methods(cf. WO 98/35 553, WO 00/35 278 and EP-A 0 681 865).

Suitable penetration enhancers also include, for example, substanceswhich promote the availability of the compounds of the formula (I) inthe spray coating. Those include, for example, mineral or vegetableoils. Suitable oils are all mineral or vegetable oils—modified orotherwise—which can typically be used in agrochemical compositions.Mention may be made by way of example of sunflower oil, rapeseed oil,olive oil, castor oil, cloza oil, maize seed oil, cotton seed oil andsoya bean oil, or the esters of said oils. Preference is given torapeseed oil, sunflower oil and their methyl or ethyl esters.

The concentration of penetration enhancer in the compositions of theinvention can be varied within a wide range. In the case of a formulatedcrop protection composition it is in general 1% to 95%, preferably 1% to55%, more preferably 15%-40% by weight. In the ready-to-use compositions(spray liquors) the concentrations are generally between 0.1 and 10 g/l,preferably between 0.5 and 5 g/l.

Crop protection compositions of the invention may also comprise furthercomponents, examples being surfactants and/or dispersing assistants oremulsifiers.

Suitable nonionic surfactants and/or dispersing assistants include allsubstances of this type that can typically be used in agrochemicalcompositions. Preferably mention may be made of polyethyleneoxide-polypropylene oxide block copolymers, polyethylene glycol ethersof linear alcohols, reaction products of fatty acids with ethylene oxideand/or propylene oxide, and also polyvinyl alcohol,polyvinylpyrrolidone, copolymers of polyvinyl alcohol andpolyvinylpyrrolidone, and copolymers of (meth)acrylic acid and(meth)acrylic esters, and additionally alkyl ethoxylates and alkylarylethoxylates, which optionally may be phosphated and optionally may beneutralized with bases, mention being made, by way of example, ofsorbitol ethoxylates, and also polyoxyalkylenamine derivatives.

Suitable anionic surfactants include all substances of this type thatcan typically be used in agrochemical compositions. Preference is givento alkali metal salts and alkaline earth metal salts of alkylsulphonicacids or alkylarylsulphonic acids.

A further preferred group of anionic surfactants and/or dispersingassistants are the following salts that are of low solubility in plantoil; salts of polystyrenesulphonic acids, salts of polyvinylsulphonicacids, salts of naphthalenesulphonic acid-formaldehyde condensationproducts, salts of condensation products of naphthalenesulphonic acid,phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.

Suitable additives which may be included in the formulations of theinvention are emulsifiers, foam inhibitors, preservatives, antioxidants,dyes and inert filling materials.

Preferred emulsifiers are ethoxylated nonylphenols, reaction products ofalkylphenols with ethylene oxide and/or propylene oxide, ethoxylatedarylalkylphenols, and also ethoxylated and propoxylatedarylalkylphenols, and also sulphated or phosphated arylalkyl ethoxylatesand/or arylalkyl ethoxypropoxylates, mention being made by way ofexample of sorbitan derivatives, such as polyethylene oxide-sorbitanfatty acid esters, and sorbitan fatty acid esters.

Using, for example, according to method (A), ethylN-(2,6-dimethyl-4-trifluoroethoxyphenylacetyl)-1-aminocyclohexanecarboxylate as the starting material, the course of themethod according to the invention can be illustrated by the followingreaction scheme:

Using, for example, according to method (B), ethylO-(2,6-dimethyl-4-trifluoroethoxyphenylacetyl)-2-hydroxyisobutyrate, thecourse of the method according to the invention can be illustrated bythe following reaction scheme:

Using, for example, according to method (C), ethyl2-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-(4-methoxy)benzylmercapto-4-methyl-3-oxovalerate,the course of the method according to the invention can be illustratedby the following reaction scheme:

Using, for example, according to method (D), chlorocarbonyl,2,6-dimethyl-4-trifluoroethoxyphenyl ketene and acetone as startingcompounds, the course of the method according to the invention can beillustrated by the following reaction scheme:

Using, for example, according to method (E), chlorocarbonyl2,6-dimethyl-4-trifluoroethoxyphenyl ketene and thiobenzamide asstarting compounds, the course of the method according to the inventioncan be illustrated by the following reaction scheme:

Using, for example, according to method (F), ethyl5-(2,6-dimethyl-4-trifluoroethoxyphenyl)-2,3-trimethylene-4-oxovalerate,the course of the method according to the invention can be illustratedby the following reaction scheme:

Using, for example, according to method (G), ethyl6-[(2,6-dimethyl-4-trifluoroethoxy)phenyl]-2-dimethyl-5-oxohexanoate,the course of the method according to the invention can be illustratedby the following reaction scheme:

Using, for example, according to method (Hα), hexahydropyridazine andchlorocarbonyl 2,6-dimethyl-4-trifluoroethoxyphenyl ketene as startingcompounds, the course of reaction in the method according to theinvention can be illustrated by the following reaction scheme:

Using, for example, according to method (Hβ), hexahydropyridazine anddimethyl 2-(2,6-dimethyl-4-trifluoroethoxy)phenylmalonate as startingmaterials, the course of the method according to the invention can beillustrated by the following reaction scheme:

Using, for example, according to method (Hγ),1-ethoxycarbonyl-2-[(2,6-dimethyl-4-trifluoroethoxy)phenylacetyl]hexahydropyridazineas the starting material, the course of reaction can be illustrated bythe following scheme:

Using, for example, according to method (I), ethylN-(2,6-dimethyl-4-trifluoroethoxyphenylacetyl)-1-aminomethylcyclohexanecarboxylateas the starting material, the course of the method according to theinvention can be illustrated by the following reaction scheme:

Using, for example, according to method (J), ethylO-(2,6-dimethyl-4-trifluoroethoxyphenylacetyl)-3-hydroxy-2,2-dimethylpropionate,the course of the method according to the invention can be illustratedby the following reaction scheme:

Using according to method (K), ethylN-methyl-N-[(2,6-dimethyl-4-trifluoroethoxy)phenylacetyl]-1-aminooxycyclopentanecarboxylateas the starting material, the course of the method according to theinvention can be illustrated by the following reaction scheme:

Using, for example, according to method (Lα),3-(2-methyl-4-trifluroethoxy-6-ethylphenyl)-5,5-dimethylpyrrolidine-2,4-dioneand pivaloyl chloride as starting materials, the course of the methodaccording to the invention can be illustrated by the following reactionscheme:

Using, for example, according to method (Lβ),3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-5,5-dimethylpyrrolidine-2,4-dioneand acetic anhydride as starting compounds, the course of the methodaccording to the invention can be illustrated by the following reactionscheme:

Using, for example, according to method (M),8-[(2,6-dimethyl-4-trifluoroethoxy)phenyl]-1-azabicyclo[4.3.0^(1.6)]nonane-7,9-dioneand ethyl chloroformate as starting compounds, the course of the methodaccording to the invention can be illustrated by the following reactionscheme:

Using, for example, according to method (N),3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5-methyl-6-(phenyl)pyroneand methyl chloromonothioformate as starting materials, the course ofreaction can be illustrated as follows:

Using, for example, according to method (O),3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-5,5-pentamethylenepyrrolidine-2,4-dioneand methanesulphonyl chloride as starting materials, the course ofreaction can be illustrated by the following reaction scheme:

Using, for example, according to method (P),3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5,5-dimethylpyrrolidine-2,4-dioneand 2,2,2-trifluoroethyl methanethiophosphonyl chloride as startingmaterials, the course of reaction can be illustrated by the followingreaction scheme:

Using, for example, according to method (Q),3-(2-ethyl-4-trifluoroethoxy-6-methylphenyl]-5-cyclopropyl-5-methylpyrrolidine-2,4-dioneand NaOH as components, the course of the method according to theinvention can be illustrated by the following reaction scheme:

Using, for example, according to method (R) variant α,3-(2,6-dimethyl-4-trifluoroethoxyphenyl)-4-hydroxy-5,5-tetramethylene-Δ³-dihydrofuran-2-oneand ethyl isocyanate as starting materials, the course of reaction canbe illustrated by the following reaction scheme:

Using, for example, according to method (R) variant β,3-(2-methyl-4-trifluoroethoxy-6-ethylphenyl)-5-methylpyrrolidine-2,4-dioneand dimethylcarbamyl chloride as starting materials, the course ofreaction can be illustrated by the following scheme:

Using, for example, according to method (S),3-(4-bromine-2,6-dimethylphenyl)-5,5-dimethylpyrrolidine-2,4-dione andtrifluoroethanol as starting materials, the course of reaction can beillustrated by the following scheme:

The compounds of the formula (II) required as starting materials in theprocess according to the invention (a)

in which

-   -   A, B, D, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XXVII)

in which

-   -   A, B, R⁸ and D are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y and Z are each as defined above and    -   U² is a leaving group introduced by carboxylic acid activating        reagents such as carbonyldiimidazole, carbonyldiimides (for        example dicyclohexylcarbodiimide), phosphorylating reagents (for        example POCl₃, BOP-Cl), halogenating agents, e.g. thionyl        chloride, oxalyl chloride, phosgene or chloroformic esters.    -   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem.        6, 341-5, 1968)    -   or when acylamino acids of the formula (XXIX)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above,    -   are esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of the formula (XXIX)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above    -   are novel.

The compounds of the formula (XXIX) are obtained when amino acids of theformula (XXX)

in which

-   -   A, B, and D are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y and Z are each as defined above and    -   U² is as defined above,

for example according to Schotten-Baumann (Organikum, VEB DeutscherVerlag der Wissenschaften, Berlin 1977, p. 505).

The compounds of the formula (XXVIII) are novel. They can be prepared byprocesses known in principle (see, for example, H. Henecka, Houben-Weyl,Mothoden der Organischen Chemie, Vol. 8, p. 467-469 (1952) WO 97/02243,WO 99/43699), or are obtained in situ with the above-specified reagents.

The compounds of the formula (XXVIII) are obtained, for example, byreacting substituted phenylacetic acids of the formula (XXXI)

in which

-   -   W, X, Y and Z are each as defined above,    -   with halogenating agents (e.g. thionyl chloride, thionyl        bromide, oxalyl chloride, phosgene, phosphorus trichloride,        phosphorus tribromide or phosphorus pentachloride),        phosphonylating reagents (for example POCl₃, BOP-Cl),        carbonyldiimidazole, carbonyldiimides (e.g.        dicyclohexylcarbonyldiimide), optionally in the presence of a        diluent (for example optionally chlorinated aliphatic or        aromatic hydrocarbons such as toluene or methylene chloride or        ethers, e.g. tetrahydrofuran, dioxane, methyl tert-butyl ether)        at temperatures of −20° C. to 150° C., preferably of −10° C. to        100° C.

Some of the compounds of the formula (XXVII) and (XXX) are known fromthe patent literature cited at the outset and/or can be prepared byknown processes (see, for example, Compagnon, Miocque Ann. Chim. (Paris)[14] 5, p. 11-22, 23-27 (1970)).

The substituted cyclic amino carboxylic acids of the formula (XXX) inwhich A and B form a ring are generally obtainable by the Bucherer-Bergssynthesis or by the Strecker synthesis and are obtained in differentisomeric forms in each case. Thus, under the conditions of theBucherer-Bergs synthesis, predominantly the isomers (for the sake ofsimplicity referred to hereinafter as β) in which the R radicals and thecarboxyl group are in equatorial positions are obtained, whereas, underthe conditions of the Strecker synthesis, predominantly the isomers (forthe sake of simplicity, referred to hereinafter as α) in which the aminogroup and the R radicals are in equatorial positions are obtained.

(L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.J. Chem. 53, 3339 (1975).

In addition, the starting materials of the formula (II) used in theabove method (A)

in which

-   -   A, B, D, W, X, Y, Z and R⁸ are each as defined above,    -   can be prepared when aminonitriles of the formula (XXXII)

in which

-   -   A, B and D are each as defined above,    -   are reacted with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above,    -   to give compounds of the formula (XXXIII)

in which

-   -   A, B, D, W, X, Y and Z are each as defined above,    -   and the latter are subsequently subjected to an acidic        alcoholysis.

The compounds of the formula (XXXIII) are likewise novel.

The compounds of the formula (III) required as starting materials in themethod (B) according to the invention

in which

-   -   A, B, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

They can be prepared by methods known in principle.

For example, the compounds of the formula (III) are obtained when

2-hydroxycarboxylic esters of the formula (XXXIV-A)

in which

-   -   A, B and R⁸ are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above,    -   (Chem. Reviews 52, 237-416 (1953)).

In addition, compounds of the formula (III) are obtained when

-   -   substituted phenylacetic acids of the formula (XXXI)

in which

-   -   W, X, Y and Z are each as defined above,    -   are alkylated with α-halocarboxylic esters of the formula        (XXXIV-B)

in which

-   -   A, B, and R⁸ are each as defined above and    -   Hal is chlorine or bromine.

Some of the compounds of the formula (XXXIV-A) are commerciallyavailable or known from the disclosures mentioned at the outset.

The compounds of the formula (XXXIV-B) are commercially available.

The compounds of the formula (XXXI) are novel.

For example, the compounds of the formula (XXXI) are obtained

in which

-   -   W, X, Y and Z are each as defined above,    -   when phenylacetic esters of the formula (XXXV)

in which

-   -   W, X, Y, Z and R⁸ are each as defined above,    -   are hydrolysed in the presence of acids or bases, in the        presence of a solvent, under commonly known standard conditions.

The compounds of the formula (XXXV) are novel.

The compounds of the formula (XXXV)

in which

-   -   W, X, Y, Z and R⁸ are each as defined above,    -   are obtained by the method analogous to method (S) described in        the examples,    -   when phenylacetic esters of the formula (XXXV-a)

in which

-   -   R⁸, W, X and Y are each as defined above    -   and Z′ is bromine or iodine,    -   are converted in the presence of haloalkyl alcohols (e.g.        trifluoroethanol, in the presence of a base and optionally in        the presence of a copper salt (preferably Cu(I)I).

The phenylacetic esters of the formula (XXXV-a) are known in principle,for example, from publications WO 96/35 664, WO 97/02243, WO 97/01535,WO 98/05638 and DE-A-10 301 804, and can be prepared by the processesdescribed there.

The compounds of the formula (IV) required as starting materials in theabove method (C)

in which

-   -   A, B, V, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

They can be prepared by methods known in principle.

The compounds of the formula (IV) are obtained, for example, when

-   -   substituted phenylacetic esters of the formula (XXXV)

in which

-   -   W, X, Y, Z and R⁸ are each as defined above.    -   are acylated with 2-benzylthiocarbonyl halides of the formula        (XXXVI)

in which

-   -   A, B and V are each as defined above and    -   Hal is halogen (especially chlorine or bromine),    -   in the presence of strong bases (see for example, M. S.        Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem.        Commun., (1987), 1228).

Some of the benzylthiocarbonyl halides of the formula (XXXVI) are knownand/or can be prepared by known processes (J. Antibiotics (1983), 26,1589).

The halocarbonyl ketenes of the formula (VI) required as startingmaterials in the above methods (D), (E) and (H-α) are novel. They can beprepared by methods known in principle (cf., for example, Org. Prep.Proced. Int., 7, (4), 155-158, 1975 and DE 1 945 703). For example, thecompounds of the formula (VI)

in which

-   -   W, X, Y and Z are each as defined above and    -   Hal is chlorine or bromine    -   are obtained when    -   substituted phenylmalonic acids of the formula (XXXVII)

in which

-   -   W, X, Y and Z are each as defined above.    -   are reacted with acid halides, for example thionyl chloride,        phosphorus(V) chloride, phosphorus(III) chloride, oxalyl        chloride, phosgene or thionyl bromide, optionally in the        presence of catalysts, for example dimethylformamide,        methylstearylformamide or triphenylphosphine, and optionally in        the presence of bases, for example pyridine or triethylamine.

The substituted phenylmalonic acids of the formula (XXXVII) are novel.They can be prepared in a simple manner by known processes (cf., forexample, Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin1977, p. 517 ff, EP-A-528 156, WO 06/35 664, WO 97/02 243, WO 97/01535,WO 97/36868 and WO 98/05638).

For instance, phenylmalonic acids of the formula (XXXVII)

in which

-   -   W, X, Y and Z are each as defined above.    -   are obtained when phenylmalonic esters of the formula (XI)

in which

-   -   W, X, Y and Z are each as defined above,    -   and U¹ is OR⁸,    -   where R⁸ is as defined above,    -   are first hydrolysed in the presence of a base and a solvent and        then acidified cautiously (see, for example, EP-A-528 156, WO        96/35 664, WO 97/02 243).

The malonic esters of the formula (XI)

in which

-   -   W, X, Y and Z are each as defined above,    -   and U¹ is OR⁸,    -   where R⁸ is as defined above

are novel.

They can be prepared by commonly known methods of organic chemistry (of,for example, Tetrahedron Lett. 27, 2763 (1986), Organikum VEB DeutscherVerlag der Wissenschaften, Berlin 1977, p. 587 ff., WO 96/35664, WO97/02243, WO 97/01535, WO 97/36868, WO 98/05638 and WO 99/47525).

The carbonyl compounds of the formula (V) required as starting materialsfor the method (D) according to the invention

in which

-   -   A and D are each as defined above,    -   or the silyl enol ethers thereof, of the formula (Va)

in which

-   -   A, D and R⁸ are each as defined above,

are commercially available, commonly known compounds, or compoundsobtainable by known processes.

The principle of preparation of the ketenyl chlorides of the formula(VI) required as starting materials to perform the method (E) accordingto the invention has already been described in connection with method D.The thioamides of the formula (VII) required to perform the method (E)according to the invention

in which

-   -   A is as defined above.    -   are compounds which are common knowledge in organic chemistry.

The compounds of the formula (VIII) required as starting materials inthe above method (F)

in which

-   -   A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above.    -   are novel.

They can be prepared by methods known in principle.

The 5-aryl-4-ketocarboxylic esters of the formula (VIII) are obtained,for example, when 5-aryl-4-ketocarboxylic aids of the formula (XXXVIII)

in which

-   -   W, X, Y, Z, A, B, Q¹ and Q² are each as defined above,    -   are esterified (cf., for example, Organikum, 15th edition,        Berlin, 1977, page 499) or alkylated (see preparation example).

The 5-aryl-4-ketocarboxylic acids of the formula (XXXVIII)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above,    -   are novel, but can be prepared by methods known in principle (WO        96/01 798, WO 97/14667, WO 98/39281).

The 5-aryl-4-ketocarboxylic acids of the formula (XXXVIII) are obtained,for example, when 2-phenyl-3-oxoadipic esters of the formula (XXXIX)

in which

-   -   A, B, Q¹, Q², W, X, Y and Z are each as defined above and    -   R⁸ and R^(8′) are each alkyl (especially C₁-C₈-alkyl) and    -   when the compound of the formula (XLI-a) is used, R⁸ is        hydrogen,    -   are decarboxylated, optionally in the presence of a diluent and        optionally in the presence of a base or acid (cf, for example,        Organikum, 15th edition, Berlin, 1977, page 519 to 521, WO        96/01798, WO 97/14667, WO 98/39281).

The compounds of the formula (XXXIX)

in which

-   -   A, B, Q¹, Q², W, X, Y, Z, R⁸ and R^(8′) are each as defined        above and    -   when the compound of the formula (XLI-a) is used, R⁸ is        hydrogen,    -   are novel.

The compounds of the formula (XXXIX) are obtained, for example,

-   -   when dicarboxylic monoester chlorides of the formula (XL)

in which

-   -   A, B, Q¹, Q² and R⁸ are each as defined above and    -   Hal is chlorine or bromine,    -   or carboxylic anhydrides of the formula (XLI-a)

in which

-   -   A, B, Q¹ and Q² are each as defined above.    -   are acylated with a phenylacetic ester of the formula (XXXV)

in which

-   -   W, X, Y, Z and R⁸ are each as defined above,    -   in the presence of a diluent and in the presence of a base (cf,        for example, M. S. Chambers, E. J. Thomas. D. J. Williams. J        Chem. Soc. Chem. Commun., (1987), 1228; cf. also the preparation        examples).

Some of the compounds of the formulae (XL) and (XLI-a) are knowncompounds in organic chemistry and/or can be prepared in a simple mannerby methods known in principle.

The compounds of the formula (IX) required as starting materials in theabove method (G)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

They can be prepared by methods known in principle.

6-aryl-5-ketocarboxylic esters of the formula (IX) are obtained, forexample, when 6-aryl-5-ketocarboxylic acids of the formula (XLII)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y and Z are each as defined above,    -   are esterified (cf., for example, Organikum, 15th edition,        Berlin, 1977, page 499, WO 99/43649, WO 99/48869).

The 6-aryl-5-ketocarboxylic acids of the formula (XLII)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y and Z are each as defined above,    -   are novel. They can be prepared by methods known in principle        (WO 99/43649, WO 99/48869), for example when    -   substituted 2-phenyl-3-oxoheptanedioic esters of the formula        (XLIII)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X and Z are each as defined above and    -   R⁸ and R^(8′) are each alkyl (preferably C₁-C₆-alkyl), and,    -   when the compound of the formula (XLI-b) is used, R⁸ is        hydrogen,    -   are hydrolysed and decarboxylated, optionally in the presence of        a diluent and optionally in the presence of a base or acid (cf.,        for example, Organikum, 15th edition, Berlin, 1977, page 519 to        521, WO 99/43649, WO 99/48869).

The compounds of the formula (XLIII)

in which

-   -   A, B, Q⁵, Q⁶, U, W, X, Y, Z, R⁸ and R^(8′) and each as defined        above,    -   are novel and are obtainable,    -   when dicarboxylic esters of the formula (XLIV)

in which

-   -   A, B, Q⁵, Q⁶, U and R⁸ are each as defined above,    -   or carboxylic anhydrides of the formula (XLI-b)

in which

-   -   A, B, Q⁵, Q⁶ and U are each as defined above    -   are condensed with a substituted phenylacetic ester of the        formula (XXXV)

in which

-   -   W, X, Y, Z and R^(8′) are each as defined above,    -   in the presence of a diluent and in the presence of a base.

Some of the compounds of the formula (XLIV) are known and/or can beprepared by known processes.

Some of the hydrazines of the formula (X) required as starting materialsfor the method (H-α) and (H-β) according to the invention

A-NH-NH-D  (X)

in which

-   -   A and D are each as defined above,    -   are known and/or preparable by literature methods (cf., for        example, Liebigs Ann. Chem. 585, 6 (1954); Reaktionen der        organischen Synthese, C. Ferri, page 212, 513; Georg Thieme        Verlag Stuttgart, 1978; Liebigs Ann. Chem. 443, 242 (1925);        Chem. Ber. 98, 2551 (1965), EP-A-508 126, WO 92/16510, WO 99/47        525, WO 01/17 972).

The compounds of the formula (XII) required for the method (H-γ)according to the invention

in which

-   -   A, D, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

The acyl carbazates of the formula (XII) are obtained, for example, whencarbazates of the formula (XLV)

in which

-   -   A, R⁸ and D are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z, and U² are each as defined above    -   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem.        6, 341-5, 1968).

Some of the carbazates of the formula (XLV) are commercially availableand some are known compounds or can be prepared by methods of organicchemistry known in principle.

The compounds of the formula (XXVIII) have already been described forthe precursors for methods (A) and (B).

The compounds of the formula (XIII) required as starting materials inthe method (I) according to the invention

in which

-   -   A, B, D, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above are        novel.

The acylamino acid esters of the formula (XIII) are obtained, forexample, when amino acid derivatives of the formula (XLVI)

in which

-   -   A, B, Q¹, Q², R⁸ and D are each as defined above,    -   are acylated with substituted hetarylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above    -   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem.        6, 341-5, 1968)    -   or when acylamino acids of the formula (XLVII)

in which

-   -   A, B, D, Q¹, Q², W, X, Y and Z are each as defined above,    -   are esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of the formula (XLVII)

in which

-   -   A, B, D, Q¹, Q², W, X, Y and Z are each as defined above,    -   are novel.

The compounds of the formula (XLVII) are obtained when β-amino acids ofthe formula (XLVIII)

in which

-   -   A, B, Q¹, Q² and D are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above,    -   for example according to Schotten-Baumann (Organikum, VEB        Deutscher Verlag des Wissenschaften, Berlin 1977, p. 505).

Some of the compounds of the formulae (XLVI) and (XLVIII) are known fromWO 01/79204 or can be prepared by the method known in principlespecified there.

The compounds of the formula (XIV) required as starting materials in themethod (J) according to the invention

in which

-   -   A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

The acylhydroxycarboxylic esters of the formula (XIV) are obtained, forexample, when hydroxycarboxylic esters of the formula (XLIX)

in which

-   -   A, B, Q¹, Q² and R⁸ are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above    -   (see preparation examples of the formula (II)).

Some of the compounds of the formula (XLIX) are known from WO 01/98288or can be prepared by methods known in principle, for example byReformatsky synthesis (Organikum, VEB Deutscher Verlag derWissenschaften, Berlin 1990, 18th ed. p. 501 ff.)

The compounds of the formula (XV) required as starting materials in themethod (K) according to the invention

in which

-   -   A, B, D, W, X, Y, Z and R⁸ are each as defined above,    -   are novel.

The acylhydroxylamino acid esters of the formula (XV) are obtained, forexample, when amino acid derivatives of the formula (L)

in which

-   -   A, B, R⁸ and D are each as defined above,    -   are acylated with substituted phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above    -   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem.        6, 341-5, 1968).

Some of the hydroxylamino acid esters of the formula (L) required asstarting materials to prepare compounds of the formula (II)

in which

-   -   A, B and R⁸ are each as defined above are novel and can be        prepared by known processes (N. A. Porter et. al. J. Org. Chem.        63 5547 (1998), WO 03/048138).

For example, hydroxylamino acid esters of the formula (L)

in which

-   -   A, B, and R⁸ are each as defined above are obtained when        N-hydroxyphthalimide of the formula (LI)

is reacted with haloalkyl esters of the formula (LII)

in which

-   -   A, B, and R⁸ are each as defined above and    -   Hal is chlorine, bromine or iodine, preferably bromine,    -    to give O-alkoxyphthalimides of the formula (LIII),

in which

-   -   A, B, and R⁸ are each as defined above,    -   and then the compounds of the formula (L) are released, for        example by hydrazinolysis.

The compounds of the formula (LII) and (LI) are likewise known and canbe prepared by known processes (N. A. Porter et. al. J. Org. Chem. 63,5547-5554, 1998).

In addition, for example, acylhydroxylamino acid esters of the formula(XV)

in which

-   -   A, B, D, W, X, Y, Z and R⁸ are each as defined above,    -   but D is preferably not hydrogen,    -   are obtained when, for example, phenylacetic acid derivatives of        the formula (XXVIII)

in which

-   -   W, X, Y, Z and U² are each as defined above    -   are reacted with hydroxylamines of the formula (LIV)

in which

-   -   D is as defined above, but is preferably not hydrogen,    -   to give compounds of the formula (LV)

in which

-   -   D, W, X, Y and Z are each as defined above,    -   and the latter are alkylated with haloalkyl esters of the        formula (LII),

in which

-   -   A, B and R⁸ are each as defined above    -   and    -   Hal is chlorine, bromine and iodine, preferably bromine.    -   to give compounds of the formula (XV) (E. K. Ryo et. al., Bull.        Korean Chem. Soc. 20 965 (1999)).

Some of the compounds of the formula (LIV) are commercially available,some are known, and can be prepared by known methods.

Moreover, compounds of the formula (XV) in which D is not hydrogen areobtained when compounds of the formula (XV-a)

in which

-   -   A, B, W, X, Y, Z and R⁸ are each as defined above    -   are alkylated with compounds of the formula (LVI)

D-LG  (LVI)

in which

-   -   D is as defined above, but is not hydrogen,    -   and    -   LG is a leaving group, for example chlorine, bromine, iodine,        mesylate, tosylate or triflate    -   to give compounds of the formula (XV) (WO 03/048138).

Some of the compounds of the formula (LVI) are commercially available,some are known, and can be prepared by known methods.

The compounds of the formulae (LIII) and (LV) are known and arepreparable according to the literature cited at the outset.

The acid halides of the formula (XVI), carboxylic anhydrides of theformula (XVII), chloroformic esters or chloroformic thioesters of theformula (XVIII), chloromonothioformic esters or chlorodithioformicesters of the formula (XIX), sulphonyl chlorides of the formula (XX),phosphorus compounds of the formula (XXI) and metal hydroxides, metalalkoxides or amines of the formula (XXII) and (XXIII) and isocyanates ofthe formula (XXIV) and carbamyl chloride of the formula (XXV) andhaloalkanols of the formula (XXVI) also required as starting materialsto perform the methods (L), (M), (N), (O), (P), (Q), (R) and (S)according to the invention are commonly known compounds in organic orinorganic chemistry.

The compounds of the formulae (V),(VII), (X), (XXVII), (XXX), (XXXII),(XXXIV-A), (XXXIV-V), (XXXVI), (XL), (XLI-a), (XLI-b), (XLIV), (XLV),(XLVI), (XLVIII), (XLIX), (LI), (LII), (LIV) and (LVI) are additionallyknown from the patent applications cited at the outset and/or can beprepared by the methods specified there.

The compounds of the formulae (I-1′-I-11′) can be prepared analogouslyto the methods A to R described and some are novel. The compounds of theformula (I-1′-a) are novel and can be prepared by method A. Some of thephenylacetic acids of the formula (XXXI′) required to prepare thecompounds of the formula (I-1′-a)

in which W, X, Y and Z′ are each as defined above are novel. Compoundsof the formula (XXXI′) in which Z′ is in the 3 position and Y ishydrogen are novel.

Method (A) is characterized in that compounds of the formula (II) inwhich A, B, W, X, Y, Z and R⁸ are each as defined above are subjected toan intramolecular condensation in the presence of a base.

The diluents used in method (A) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, and additionally polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide and N-methylpyrrolidone, and alsoalcohols, such as methanol, ethanol, propanol, isopropanol, butanol,isobutanol and tert-butanol.

The bases (deprotonating agents) used in the performance of method (A)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which may also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). It is additionally possible to usealkali metals, such as sodium or potassium. It is also possible toemploy alkali metal and alkaline earth metal amides and hydrides, suchas sodium amide, sodium hydride and calcium hydride, and additionallyalso alkali metal alkoxides, such as sodium methoxide, sodium ethoxideand potassium tert-butoxide.

When performing method (A) according to the invention, the reactiontemperatures may be varied within a relatively wide range. In general,the temperatures employed are between 0° C. and 250° C., preferablybetween 50° C. and 150° C.

Method (A) according to the invention is generally performed underatmospheric pressure.

When performing method (A) according to the invention, the reactioncomponents of the formula (II) and the deprotonating bases are generallyemployed in about double the equimolar amounts. However, it is alsopossible to use one component or the other in a greater excess (up to 3mol).

Method (B) is characterized in that compounds of the formula (III) inwhich A, B, W, X, Y, Z and R⁸ are each as defined above are subjected toan intramolecular condensation in the presence of a diluent and in thepresence of a base.

The diluents used for the method (B) according to the invention may beany inert organic solvent.

Preference is given to using hydrocarbons, such as toluene and xylene,and also ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycoldimethyl ether and diglycol dimethyl ether, and additionally polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methylpyrrolidone. It is also possible to use alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol andtert-butanol.

The bases (deprotonating agents) used when performing method (B)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which may also be used in the presenceof phase transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine. It is also possible to use alkalimetals, such as sodium or potassium. In addition, it is possible toemploy alkali metal and alkaline earth metal amides and hydrides, suchas sodium amide, sodium hydride and calcium hydride, and additionallyalso alkali metal alkoxides, such as sodium methoxide, sodium ethoxideand potassium tert-butoxide.

When performing method (B) according to the invention, the reactiontemperatures may be varied within a relatively wide range. In general,the temperatures employed are between 0° C. and 250° C., preferablybetween 50° C. and 150° C.

Method (B) according to the invention is generally performed underatmospheric pressure.

When performing method (B) according to the invention, the reactioncomponents of the formula (III) and the deprotonating bases aregenerally employed in about equimolar amounts. However, it is alsopossible to use one component or the other in a greater excess (up to 3mol).

Method (C) is characterized in that compounds of the formula (IV) inwhich A, B, V, W, X, Y, Z and R⁸ are each as defined above areintramolecularly cyclized in the presence of an acid and optionally inthe presence of a diluent.

The diluents used in method (C) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also halogenated hydrocarbons, such asdichloromethane, chloroform, ethylene chloride, chlorobenzene,dichlorobenzene, and also polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide and N-methylpyrrolidone. It isadditionally possible to use alcohols such as methanol, ethanol,propanol, isopropanol, butanol, isobutanol, tert-butanol.

The acid used may optionally also serve as the diluent.

The acid used in method (C) according to the invention may be anycustomary inorganic or organic acid, for example hydrohalic acids,sulphuric acid, alkyl-, aryl- and haloalkylsulphonic acids, especiallyhalogenated alkylcarboxylic acids, for example trifluoroacetic acid.

The reaction temperatures when performing method (C) according to theinvention may be varied within a relatively wide range. In general, thetemperatures employed are between 0° C. and 250° C., preferably between50° C. and 150° C.

Method (C) according to the invention is generally performed underatmospheric pressure.

When performing method (C) according to the invention, the reactioncomponents of the formula (IV) and the acid are used, for example, inequimolar amounts. However, it is also possible in some cases to use theacid as the solvent or as the catalyst.

Method (D) according to the invention is characterized in that carbonylcompounds of the formula (V) or the enol ether thereof, of the formula(V-a), is reacted with ketenoyl halides of the formula (VI) in thepresence of a diluent and optionally in the presence of an acidacceptor.

The diluents used in method (D) according to the invention may be anyinert organic solvent. Preference is given to using optionallyhalogenated hydrocarbons, such as toluene, xylene, mesitylene,chlorobenzene and dichlorobenzene, and also ethers, such as dibutylether, glycol dimethyl ether, diglycol dimethyl ether and diphenylether, and also polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide or N-methylpyrrolidone.

The acid acceptors used when performing method variant (D) according tothe invention may be any customary acid acceptor.

Preference is given to using tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig's base and N,N-dimethylaniline.

The reaction temperatures when performing method variant (D) accordingto the invention can be varied within a relatively wide range. It isappropriate to work at temperatures between 0° C. and 250° C.,preferably between 50° C., and 220° C.

Method (D) according to the invention is appropriately performed underatmospheric pressure.

When performing method (D) according to the invention, the reactioncomponents of the formulae (V) and (VI) in which A, D, W, X, Y and Z areeach as defined above and Hal is halogen, and optionally the acidacceptors, are generally used in about equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 5 mol).

Method (E) according to the invention is characterized in thatthioamides of the formula (VII) are reacted with ketenoyl halides of theformula (VI) in the presence of a diluent and optionally in the presenceof an acid acceptor.

The diluents used in method variant (E) according to the invention maybe any inert organic solvent. Preference is given to using hydrocarbons,such as toluene and xylene, and also ethers, such as dibutyl ether,glycol dimethyl ether and diglycol dimethyl ether, and also polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methylpyrrolidone.

The acid acceptors used when performing method (E) according to theinvention may be any customary acid acceptor.

Preference is given to using tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig's base and N,N-dimethylaniline.

The reaction temperatures when performing method (E) according to theinvention can be varied within a relatively wide range. It isappropriate to work at temperatures between 0° C. and 250° C.,preferably between 20° C. and 220° C.

Method (E) according to the invention is appropriately performed underatmospheric pressure.

When performing method (E) according to the invention, the reactioncomponents of the formulae (VII) and (VI) in which A, W, X, Y and Z areeach as defined above and Hal is halogen and optionally the acidacceptors are generally used in about equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 5 mol).

Method (F) is characterized in that compounds of the formula (VIII) inwhich A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of a base.

The diluents used in method (F) according to the invention may be anyorganic solvent inert toward the reaction participants. Preference isgiven to using hydrocarbons, such as toluene and xylene, and alsoethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethylether and diglycol dimethyl ether, and also polar solvents, such ascollidine, dimethyl sulphoxide, sulpholane, dimethylformamide andN-methylpyrrolidone. It is additionally possible to use alcohols such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol,tert-butanol.

The bases (deprotonating agents) used when performing method (F)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(tris(methoxyethoxyethyl)amine). In addition, alkali metals such assodium or potassium can be used. Additionally usable are alkali metaland alkaline earth metal amides and hydrides, such as sodium amide,sodium hydride and calcium hydride, and additionally also alkali metalalkoxides such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide.

The reaction temperatures when performing method (F) according to theinvention can be varied within a relatively wide range. In general, thetemperatures employed are between −75° C. and 250° C., preferablybetween −50° C. and 150° C.

Method (F) according to the invention is generally performed underatmospheric pressure.

When performing method (F) according to the invention, the reactioncomponents of the formula (VIII) and the depronating bases are generallyused in about equimolar amounts. However, it is also possible to use oneor the other component in a greater excess (up to 3 mol).

Method (G) is characterized in that compounds of the formula (IX) inwhich A, B, Q⁵, Q⁶, U, W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of bases.

The diluents used in method (G) according to the invention may be anyorganic solvent inert toward the reaction participants. Preference isgiven to using hydrocarbons, such as toluene and xylene, and alsoethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethylether and diglycol dimethyl ether, and also polar solvents, such asdimethyl sulphoxide, sulpholane, dimethylformamide andN-methylpyrrolidone. It is additionally possible to use alcohols such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol,tert-butanol.

The bases (deprotonating agents) used when performing method (G)according to the invention may be any customary proton acceptor.

Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(tris(methoxyethoxyethyl)amine). In addition, alkali metals such assodium or potassium can be used. Additionally usable are alkali metaland alkaline earth metal amides and hydrides, such as sodium amide,sodium hydride and calcium hydride, and additionally also alkali metalalkoxides such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide.

The reaction temperatures when performing method (G) according to theinvention can be varied within a relatively wide range. In general, thetemperatures employed are between 0° C. and 250° C., preferably between50° C. and 150° C.

Method (G) according to the invention is generally performed underatmospheric pressure.

When performing method (G) according to the invention, the reactioncomponents of the formula (IX) and the depronating bases are generallyused in about equimolar amounts. However, it is also possible to use oneor the other component in a greater excess (up to 3 mol).

Method (H-α) according to the invention is characterized in thathydrazines of the formula (X) or salts of these compounds are reactedwith ketenoyl halides of the formula (VI) in the presence of a diluentand optionally in the presence of an acid acceptor.

The diluents used in method (H-α) according to the invention may be anyinert organic solvent. Preference is given to using optionallychlorinated hydrocarbons, for example mesitylene, chlorobenzene anddichlorobenzene, toluene, xylene, and also ethers, such as dibutylether, glycol dimethyl ether, diglycol dimethyl ether anddiphenylethane, and also polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide or N-methylpyrrolidone.

The acid acceptors used when performing method variant (H-α) accordingto the invention may be any customary acid acceptor.

Preference is given to using tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig's base and N,N-dimethylaniline.

The reaction temperatures when performing method variant (H-α) accordingto the invention may be varied within a relatively wide range. It isappropriate to work at temperatures between 0° C. and 250° C.,preferably between 50° C. and 220° C.

Method (H-α) according to the invention is appropriately performed underatmospheric pressure.

When performing method (H-α) according to the invention, the reactioncomponents of the formulae (VI) and (X) in which A, D, W, X, Y and Z areeach as defined above and Hal is halogen, and optionally the acidacceptors, are generally used in about equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 5 mol).

Method (H-β) is characterized in that hydrazines of the formula (X) orsalts of this compound, in which A and D are each as defined above, aresubjected to a condensation with malonic esters or malonamides of theformula (XI) in which U¹, W, X, Y, Z and R⁸ are each as defined above,in the presence of a base.

The diluents used in method (H-β) according to the invention may be anyinert organic solvent. Preference is given to using optionallyhalogenated hydrocarbons, such as toluene, xylene, mesitylene,chlorobenzene and dichlorobenzene, and also ethers, such as dibutylether, tetrahydrofuran, dioxane, diphenyl ether, glycol dimethyl etherand diglycol dimethyl ether, and also polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and also alcohols such as methanol, ethanol,propanol, isopropanol, butanol, isobutanol and tert-butanol.

The bases (deprotonating agents) used when performing method (H-β)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). It is additionally possible to usealkali metals such as sodium or potassium. It is also possible to usealkali metal and alkaline earth metal amides and hydrides, such assodium amide, sodium hydride and calcium hydride, and additionally alsoalkali metal alkoxides, such as sodium methoxide, sodium ethoxide andpotassium tert-butoxide.

It is also possible to use tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU),diazabicyclononene (DBN), Hünig's base and N,N-dimethylaniline.

The reaction temperatures when performing method (H-β) according to theinvention can be varied within a relatively wide range. In general, thetemperatures employed are between 0° C. and 280° C., preferably between50° C. and 180° C.

The method (H-β) according to the invention is generally performed underatmospheric pressure.

When performing method (H-β) according to the invention, the reactioncomponents of the formula (XI) and (X) are generally used in aboutequimolar amounts. However, it is also possible to use one or the othercomponent in a greater excess (up to 3 mol).

Method (H-γ) is characterized in that compounds of the formula (XII) inwhich A, D, W, X, Y, Z and R⁸ are each as defined above are subjected toan intramolecular condensation in the presence of a base.

The diluents used in method (H-γ) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, and also polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol andtert-butanol.

The bases (deprotonating agents) used when performing method (H-γ)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine. It is additionally possible to usealkali metals such as sodium or potassium. It is also possible to usealkali metal and alkaline earth metal amides and hydrides, such a sodiumamide, sodium hydride and calcium hydride, and additionally also alkalimetal alkoxides, such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide.

The reaction temperatures when performing method (H-γ) according to theinvention can be varied within a relatively wide range. In general, thetemperatures employed are between 0° C. and 250° C., preferably between50° C. and 150° C.

Method (H-γ) according to the invention is generally performed underatmospheric pressure.

When performing method (H-γ) according to the invention, the reactioncomponents of the formula (XII) and the deprotonating bases aregenerally used in about double the equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 3 mol).

Method (I) is characterized in that compounds of the formula (XIII) inwhich A, B, D, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of a base.

The diluents used in method (I) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, and also polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol andtert-butanol.

The bases (deprotonating agents) used when performing method (J)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysis, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine. It is additionally possible to usealkali metals such as sodium or potassium. It is also possible to usealkali metal and alkaline earth metal amides and hydrides, such assodium amide, sodium hydride and calcium hydride, and additionally alsoalkali metal alkoxides, such as sodium methoxide, sodium ethoxide andpotassium tert-butoxide.

The reaction temperatures when performing method (I) according to theinvention can be varied within a relatively wide range. In general, thetemperatures employed are between −80° C. and 180° C., preferablybetween −50° C. and 120° C.

Method (I) according to the invention generally performed underatmospheric pressure.

When performing method (I) according to the invention, the reactioncomponents of the formula (XIII) and the deprotonating bases aregenerally used in about double the equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 3 mol).

Method (J) is characterized in that compounds of the formula (XIV) inwhich A, B, Q¹, Q², W, X, Y, Z and R⁸ are each as defined above aresubjected to an intramolecular condensation in the presence of a base.

The diluents used in method (J) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, and also polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol andtert-butanol.

The bases (deprotonating agents) used when performing method (J)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine. It is additionally possible to usealkali metals such as sodium or potassium. It is also possible to usealkali metal and alkaline earth metal amides and hydrides, such assodium amide, sodium hydride and calcium hydride, and additionally alsoalkali metal alkoxides, such as sodium methoxide, sodium ethoxide andpotassium tert-butoxide.

The reaction temperatures when performing method (J) according to theinvention may be varied within a relatively wide range. In general,temperatures between 0° C. and 250° C., preferably between 50° C. and150° C., are employed.

Method (J) according to the invention is generally performed underatmospheric pressure.

When performing method (J) according to the invention, the reactioncomponents of the formula (XIV) and the deprotonating bases aregenerally used in about double the equimolar amounts. However, it isalso possible to use one or the other component in a greater excess (upto 3 mol).

Method (K) is characterized in that compounds of the formula (XV) inwhich A, B, D, W, X, Y, Z and R⁸ are each as defined above are subjectedto an intramolecular condensation in the presence of a base.

The diluents used in method (K) according to the invention may be anyinert organic solvent. Preference is given to using hydrocarbons, suchas toluene and xylene, and also ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, and also polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone, and also alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, isobutanol andtert-butanol.

The bases (deprotonating agents) used when performing method (K)according to the invention may be any customary proton acceptor.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase transfer catalysts, for example triethylbenzylammoniumchloride, tetrabutylammonium bromide, Adogen 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine. It is additionally possible to usealkali metals such as sodium or potassium. It is also possible to usealkali metal and alkaline earth metal amides and hydrides, such assodium amide, sodium hydride and calcium hydride, and additionally alsoalkali metal alkoxides, such as sodium methoxide, sodium ethoxide andpotassium tert-butoxide.

When performing method (K) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the temperatures employed are between −78° C. and 250° C., preferablybetween 0° C. and 150° C.

Method (K) according to the invention is generally performed underatmospheric pressure.

When performing method (K) according to the invention, the reactioncomponents of the formula (XV) and the deprotonating bases are generallyused in about double the equimolar amounts. However, it is also possibleto use one or the other component in a greater excess (up to 3 mol).

Method (L-α) is characterized in that compounds of the formulae (I-1-a)to (I-11-a) are each reacted with carbonyl halides of the formula (XVI),optionally in the presence of a diluent and optionally in the presenceof an acid binder.

The diluents used in method (L-α) according to the invention may be allsolvents inert toward the acid halides. Preference is given to usinghydrocarbons, such as benzine, benzene, toluene, xylene and tetralin,and also halohydrocarbons, such as methylene chloride, chloroform,carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and alsoketones, such as acetone and methyl isopropyl ketone, and additionallyethers, such as diethyl ether, tetrahydrofuran and dioxane, andadditionally carboxylic esters, such as ethyl acetate, and also stronglypolar solvents, such as dimethyl sulphoxide and sulpholane. If thehydrolysis stability of the acid halide permits it, the reaction canalso be performed in the presence of water.

Useful acide binders in the reaction in the process according to theinvention (L-α) are any customary acid acceptor. Preference is given tousing tertiary amines, such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hünig's base and N,N-diimethylaniline, andalso alkaline earth metal oxides, such as magnesium and calcium oxide,and also alkali metal and alkaline earth metal carbonates, such assodium carbonate, potassium carbonate and calcium carbonate, and alsoalkali metal hydroxides such as sodium hydroxide and potassiumhydroxide.

The reaction temperatures in method (L-α) according to the invention maybe varied within a relatively wide range. In general, the temperaturesemployed are between −20° C. and +150° C., preferably between 0° C. and100° C.

When performing method (L-α) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-11-a) and the carbonyl halide ofthe formula (XVI) are generally used each in approximately equivalentamounts. However, it is also possible to use the carbonyl halide in agreater excess (up to 5 mol). The workup is effected by customarymethods.

Method (L-β) is characterized in that compounds of the formulae (I-1-a)to (I-11-a) are reacted with carboxylic anhydrides of the formula(XVII), optionally in the presence of a diluent and optionally in thepresence of an acid binder.

The diluents used in method (L-β) according to the invention arepreferably those diluents which are also preferably considered when acidhalides are used. Otherwise, a carboxylic anhydride used in excess mayfunction simultaneously as a diluent.

Useful acid binders optionally added in method (L-β) are preferablythose acid binders which are preferably also considered when acidhalides are used.

The reaction temperatures in method (L-β) according to the invention canbe varied within a relatively wide range. In general, the temperaturesemployed are between −20° C. and +150° C., preferably between 0° C. and100° C.

When performing method (L-β) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-11-a) and the carboxylicanhydride of the formula (XVII) are generally each used in approximatelyequivalent amounts. However, it is also possible to use the carboxylicanhydride in a greater excess (up to 5 mol). The workup is effected bycustomary methods.

In general, diluent and excess carboxylic anhydride and the carboxylicacid formed are removed by distillation or by washing with an organicsolvent or with water.

Method (M) is characterized in that compounds of the formulae (I-1-a) to(I-11-a) are in each case reacted with chloroformic esters orchloroformic thioesters of the formula (XVIII), optionally in thepresence of a diluent and optionally in the presence of an acid binder.

Suitable acid binders for the reaction in method (M) according to theinvention are any customary acid acceptor. Preference is given to usingtertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBA,Hünig's base and N,N-dimethylaniline, and also alkaline earth metaloxides, such as magnesium oxide and calcium oxide, and also alkali metaland alkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate, and also alkali metal hydroxides, suchas sodium hydroxide and potassium hydroxide.

Suitable diluents for use in method (M) according to the invention areany solvents which are inert towards the chloroformic esters orchloroformic thioesters. Preference is given to using hydrocarbons, suchas benzine, benzene, toluene, xylene and tetralin, and also halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones,such as acetone and methyl isopropyl ketone, and also ethers, such asdiethyl ether, tetrahydrofuran and dioxane, and additionally carboxylicesters, such as ethyl acetate, and also strongly polar solvents, such asdimethyl sulphoxide and sulpholane.

When performing method (M) according to the invention, the reactiontemperatures can be varied within a relatively wide range. If the methodis performed in the presence of a diluent and an acid binder, thereaction temperatures are generally between −20° C. and +100° C.,preferably between 0° C. and 50° C.

Method (M) according to the invention is generally performed underatmospheric pressure.

When performing method (M) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-11-a) and the appropriatechloroformic ester or chloroformic thioester of the formula (XVIII) aregenerally each employed in approximately equivalent amounts. However, itis also possible to use one component or the other in a greater excess(up to 2 mol). Workup is performed by customary methods. In general,precipitated salts are removed and the reaction mixture that remains isconcentrated by removing the diluent under reduced pressure.

Method (N) according to the invention is characterized in that compoundsof the formulae (I-1-a) to (I-11-a) are in each case reacted withcompounds of the formula (XIX) in the presence of a diluent andoptionally in the presence of an acid binder.

In preparation method (N), about 1 mol of chloromonothioformic ester orchlorodithioformic ester of the formula (XIX) is reacted per mole of thestarting compound of the formulae (I-1-a) to (I-11-a) from 0 to 120° C,preferably from 20 to 60° C.

Suitable diluents which are added optionally are any inert polar organicsolvent, such as ethers, amides, sulphones, sulphoxides, and alsohalogenated alkanes.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-11-a) is prepared by addition of strong deprotonating agents, forexample sodium hydride or potassium tert-butoxide, the further additionof acid binders may be dispensed with.

If acid binders are used, these are customary inorganic or organicbases; examples include sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine and triethylamine.

The reaction may be performed at atmospheric pressure or under elevatedpressure, preference being given to working at atmospheric pressure.Workup is performed by customary methods.

Method (O) according to the invention is characterized in that compoundsof the formulae (I-1-a) to (I-11-a) are in each case reacted withsulphonyl chlorides of the formula (XX), optionally in the presence of adiluent and optionally in the presence of an acid binder.

In preparation method (O), about 1 mol of sulphonyl chloride of theformula (XX) is reacted per mole of the starting compound of theformulae (I-1-a) to (I-11-a) at from −20 to 150° C., preferably from 20to 70° C.

Useful diluents which are optionally added are any inert polar organicsolvent, such as ethers, amides, nitriles, sulphones, sulphoxides orhalogenated hydrocarbons, such as methylene chloride.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide, methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-11-a) is prepared by addition of strong deprotonating agents (forexample sodium hydride or potassium tert-butoxide), the further additionof acid binders may be dispensed with.

If acid binders are used, these are customary inorganic or organicbases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine and triethylamine.

The reaction may be performed at atmospheric pressure or under elevatedpressure and is preferably performed at atmospheric pressure. Workup isperformed by customary methods.

Method (P) according to the invention is characterized in that compoundsof the formulae (I-1-a) to (I-11-a) are reacted with phosphoruscompounds of the formula (XXI), optionally in the presence of a diluentand optionally in the presence of an acid binder.

In preparation method (P), to obtain compounds of the formulae (I-1-e)to (I-11-e), from 1 to 2, preferably from 1 to 1.3, mol of thephosphorus compound of the formula (XXI) are reacted per mole of thecompounds (I-1-a) to (I-11-a), at temperatures between −40° C. and 150°C., preferably between −10 and 110° C.

Suitable diluents which are added optionally are any inert polar organicsolvent, such as ethers, amides, nitriles, alcohols, sulphides,sulphones, sulphoxides, etc.

Preference is given to using acetonitrile, dimethyl sulphoxide,tetrahydrofuran, dimethylformamide, methylene chloride.

Suitable acid binders which are optionally added are customary inorganicor organic bases, such as hydroxides, carbonates or amines. Examplesinclude sodium hydroxide, sodium carbonate, potassium carbonate,pyridine and triethylamine.

The reaction can be performed at atmospheric pressure or under elevatedpressure and is preferably performed at atmospheric pressure. Workup isperformed by customary methods of organic chemistry. The resulting endproducts are preferably purified by crystallization, chromatographicpurification or “incipient distillation”, i.e. removal of the volatilecomponents under reduced pressure.

Method (Q) is characterized in that compounds of the formulae (I-1-a) to(I-11-a) are reacted with metal hydroxides or metal alkoxides of theformula (XXII) or amines of the formula (XXII), optionally in thepresence of a diluent.

Suitable diluents for use in method (Q) according to the invention are,preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, orelse alcohols, such as methanol, ethanol, isopropanol, and also water.

Method (Q) according to the invention is generally performed underatmospheric pressure.

The reaction temperatures are generally between −20° C. and 100° C.,preferably between 0° C. and 50° C.

Method (R) according to the invention is characterized in that compoundsof the formulae (I-1-a) to (I-11-a) are reacted in each case with (R-α)compounds of the formula (XXIV), optionally in the presence of a diluentand optionally in the presence of a catalyst, or (R-β) with compounds ofthe formula (XXV), optionally in the presence of a diluent andoptionally in the presence of an acid binder.

In preparation method (R-α), about 1 mol of isocyanate of the formula(XXIV) is reacted per mole of starting compound of the formulae (I-1-a)to (I-11-a), at from 0 to 100° C., preferably from 20 to 50° C.

Suitable diluents which are added optionally are any inert organicsolvent, such as ethers, amides, nitriles, sulphones or sulphoxides.

Optionally, catalysts may be added to accelerate the reaction. Suitablefor use as catalysts are, very advantageously, organotin compounds, forexample dibutyltin dilaurate. The reaction is preferably performed atatmospheric pressure.

In preparation method (R-β), about 1 mol of carbamoyl chloride of theformula (XXV) is reacted per mole of starting compound of the formulae(I-1-a) to (I-11-a), at from −20 to 150° C., preferably at from 0 to 70°C.

Suitable diluents which are added optionally are any inert polar organicsolvent, such as ethers, amides, sulphones, sulphoxides or halogenatedhydrocarbons.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran,dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-11-a) is prepared by addition of strong deprotonating agents (forexample sodium hydride or potassium tert-butoxide), the further additionof acid binders may be dispensed with.

If acid binders are used, they are customary inorganic or organic bases,for example sodium hydroxide, sodium carbonate, potassium carbonate,triethylamine or pyridine.

The reaction can be performed at atmospheric pressure or under elevatedpressure and is preferably performed at atmospheric pressure. Workup isperformed by customary methods.

Method (S) is characterized in that compounds of the formulae (I-1′) to(I-11′) in which A, B, D, G, Q¹, Q², U, Q⁵, Q⁶, W, X and Y are each asdefined above and Z′ is preferably bromine or iodine are reacted withalcohols of the formula ZOH in which Z is as defined above, in thepresence of a base and of Cu(I) salt (e.g. CuBr or CuI).

The diluents used in method (S) according to the invention may be anyorganic solvent inert toward the reaction participants. Preference isgiven to using hydrocarbons, such as toluene and xylene, and alsoethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethylether and diglycol dimethyl ether, and also polar solvent, such ascollidine, dimethyl sulphoxide, sulpholane, dimethylformamide,dimethylacetamide and N-methylpyrrolidone, esters such as methylacetate, ethyl acetate, propyl acetate, and alcohols of the formula WOH,for example methanol, ethanol, propanol, isopropanol, butanol andisobutanol.

The bases (deprotonating agents) used when performing method (S)according to the invention may be any customary proton acceptor.Preference is given to using alkali metals such as sodium or potassium.It is additionally possible to use alkali metal and alkaline earth metalamides and hydrides, such as sodium amide, sodium hydride and calciumhydride, and preferably also alkali metal alkoxides such as sodiummethoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxideand potassium tert-butoxide.

The reaction temperature when performing method (S) according to theinvention may be varied within a relatively wide range. In general, thetemperatures employed are between 0° C. and 250° C., preferably between50° C. and 150° C.

Method (S) according to the invention is generally performed underatmospheric pressure.

When performing method (S) according to the invention, the reactioncomponent of the formula (I-1′) to (I-11′) is generally reacted withexcesses of the alcohols ZOH and of the bases of up to 20 mol,preferably 3 to 5 mol. The copper(I) salts are generally used incatalytic amounts; 0.001 to 0.5 mol, preferably 0.01 to 0.2 mol.However, it is also possible to use them in equimolar amounts.

The inventive active ingredients are suitable, given good plantcompatibility, favourable toxicity to warm-blooded animals and goodenvironmental compatibility, for protecting plants and plant organs, forincreasing harvest yields, improving the quality of the harvest and forcontrolling animal pests, especially insects, aracnids, helminthes,nematodes and molluscs, which are encountered in agriculture, inhorticulture, in animal breeding, in forests, in gardens and leisurefacilities, in the protection of stored products and materials, and inthe hygiene sector. They can preferably be used as crop protectioncompositions. They are active against normally sensitive and resistantspecies, and against all or some stages of development. Theabovementioned pests include:

From the phylum Mollusca, for example from the class of theLamellibranchiata, for example Dreissena spp.

From the class of the Gastropoda, for example Arion spp., Biomphalariaspp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp.,Oncomelania spp., Pomacea spp., Succinea spp.

From the phylum Arthropoda, for example from the order of the Isopoda,for example Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

From the class of the Arachnida, for example Acarus spp., Aceriasheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychusviennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobiapraetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides pteronyssius, Dermatophagoides farinae, Dermacentorspp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp.,Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalommaspp., Exodes spp., Latrodectus spp., Loxoseeles spp., Metatetranychusspp., Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssusspp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemuslatus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptesspp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychusspp., Vaejovis spp., Vasates lycopersici.

From the order of the Symphyla, for example Scutigerella spp.

From the order of the Chilopoda, for example Geophilus spp., Scutigeraspp.

From the order of the Collembola, for example Onychiurus armatus.

From the order of the Diplopoda, for example Blaniulus guttulatus.

From the order of the Zygentoma, for example Lepisma saccharina,Thermobia domestica.

From the order of the Orthoptera, for example Acheta domesticus, Blattaorientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp.,Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta spp.,Pulex irritans, Schistocerca gregaria, Supella longipalpa.

From the order of the Isoptera, for example Coptotermes spp.,Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermesobesi, Odontotermes spp., Reticulitermes spp.,

From the order of the Heteroptera, for example Anasa tristis,Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylommalivida, Cavelerius spp., Cimex lectularius, Collaria spp., Creontiadesdilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti,Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp.,Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygusspp., Macropes excavatus, Miridae, monalonion atratum, Nezara spp.,Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallusspp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis,Scaptocoris castanca, Scotinophora spp., Stephanitis nashi, Tibracaspp., Triatoma spp.

From the order of the Anoplura (Phthiraptera), for example Damaliniaspp., Haematopinus spp., Linognathus spp., Pediculus spp., Ptirus pubis,Trichodectes spp.

From the order of the Homoptera, for example Acyrthosipon spp.,Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp.,Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphiscardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridiaapicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthumsolani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp.,Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida,Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphonfragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphisjuglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli,Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp.,Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccusspp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelisbilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp.,Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerusspp., Idioscopus spp., Laodelphax striatellus, Lecanium spp.,Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp.,Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monelliacostalis, monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri,Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Ortheziapraelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp.,Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzuspasserinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae,Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona,Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp.,Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphumspp., Saissetia spp., Scaphoides titanus, Schizaphis graminum,Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodesspp., Stictocephala festina, Tenalaphara malayensis, Tinocalliscaryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes spp., Triozaspp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.

From the order of the Coleoptera, for example Acalymma vittatum,Acanthoscelides obtectus, Adoretos spp., Agelastica alni, Agriotes spp.,Alphitobius diaperinus, Amphimallon solstitialis, anobium punctatum,Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogoniaspp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp.,Cassida spp., Cerotoma trifurcata, Cetorrhynchus spp., Chaetocnema spp.,Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytrazealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi,Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocisspp., Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp.,Gibbium psylloides, Hellula undalis, Heteronychus arator, Heteronyxspp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica,Hypothenemus spp., Lachnosterna consanguinea, Lema spp., Letpinotarsadecemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp.,Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp., Meligethesaeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupactusxanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilussurinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetoniajucunda, Phaedon cochleariae, Phyllophaga spp., Phyllotreta spp.,Popillia japonica, Premnotrypes spp., Prostephanus truncatus, Psylliodesspp., Ptinus spp., Rhizobias ventralis, Rhizopertha dominica, Sitophilusspp., Sphenophorus spp., Stegobium paniceum, Sternechus spp.,Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tribolium spp.,Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.

From the order of the Hymenoptera, for example Acromyrmex spp., Athaliaspp., Atta spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomoriumpharaonis, Solenopsis invicta, Tapinoma spp., Vespa spp.

From the order of the Lepidoptera, for example Acronicta major,Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyeloistransitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathrabrassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius,Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana,Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilospp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp.,Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp.,Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis,Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldanasaccharina, Ephestia spp., Epinotia spp., Epiphyas postvittana, Etiellaspp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp.,Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophilapseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella,Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodesorbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata,Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp.,Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp.,Mythimna separata, Nymphula spp., Oiketicus spp., Oria spp., Orthagaspp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp.,Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistiscitrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plodiainterpunctella, Plusia spp., Plutella xylostella, Prays spp., Prodeniaspp., Protoparce spp., Pseudaletia spp., Pseudoplusia includens,Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp.,Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp.,Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp.,Teciasolanivora, Thermesia gemmatalis, Tinea pellionella, Tineolabisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp.,Tuta absoluta, Virachola spp.

From the order of the Diptera, for example Aedes spp., Agromyza spp.,Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp.,Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata,Chironomus spp., Chrysomyia spp., Chrysops spp., Cochliomyia spp.,Contarinia spp., Cordylobia anthropophaga, Culex spp., Culicoides spp.,Culiseta spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp.,Dermatobia hominis, Drosophila spp., Echinocenemus spp., Fannia spp.,Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp.,Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Luciliaspp., Lutzomia spp., Mansonia spp., Musca spp., Nezara spp., Oestrusspp., Oscinella frit, Pegomyia spp., Phlebotomus spp., Phorbia spp.,Phormia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophagaspp., Simulium spp., Stomoxys spp., Tabanus spp., Tannia spp., Tetanopsspp., Tipula spp.

From the order of the Thysanoptera, for example Anaphothrips obscurus,Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens,Frankliniella spp., Heliothrips spp., Hercinothrips femoralis,Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni,Thrips spp.

From the order of the Siphonaptera, for example Ceratophyllus spp.,Ctenocephalides spp., Tunga penetrans, Xenopsylla cheopis.

From the phyla of the Plathelminthes and Nematodes as animal parasites,for example from the class of the Helminthes, for example Ancylostomaduodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostomaspp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp.,Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp,Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis,Echinococcus granulosus, Echinococcus multilocularis, Enterobiusvermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepisnana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomumspp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp.,Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni,Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taeniasolium, Trichinella spiralis, Trichinella nativa, Trichinella britovi,Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp.,Trichuris trichuria, Wuchereria bancrofti.

From the phylum of the Nematodes as plant pests, for exampleAphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globoderaspp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchusspp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans,Xiphinema spp.

From the subphylum of the Protozoa, for example Eimeria.

If appropriate, the inventive compounds can, at certain concentrationsor application rates, also be used as herbicides, safeners, growthregulators or agents to improve plant properties, or as microbicides,for example as fungicides, antimycotics, bactericides, viricides(including agents against viroids) or as agents against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active ingredients.

All plants and plant parts can be treated in accordance with theinvention. Plants should be understood to mean, in the present context,all plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and geneticengineering methods or by combinations of these methods, including thetransgenic plants and including the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts should be understoodto mean all parts and organs of plants above and below the ground, suchas shoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds,roots, tubers and rhizomes. The plant parts also include harvestedmaterial, and vegetative and generative propagation material, forexample cuttings, tubers, rhizomes, offshoots and seeds.

Inventive treatment of the plants and plant parts with the activeingredients is effected directly or by allowing the compounds to act ontheir surroundings, habitat or storage space by the customary treatmentmethods, for example by immersion, spraying, evaporation, fogging,scattering, painting on, injection and, in the case of propagationmaterial, in particular in the case of seeds, also by applying one ormore coats.

The active ingredients can be converted to the customary formulations,such as solutions, emulsions, wettable powders, water- and oil-basedsuspensions, powders, dusts, pastes, soluble powders, soluble granules,granules for broadcasting, suspension-emulsion concentrates, naturalmaterials impregnated with active ingredient, synthetic materialsimpregnated with active ingredient, fertilizers and microencapsulationsin polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active ingredients with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers. The formulations areprepared either in suitable plants or else before or during theapplication.

Suitable for use as auxiliaries are substances which are suitable forimparting to the composition itself and/or to preparations derivedtherefrom (for example spray liquors, seed dressings) particularproperties such as certain technical properties and/or also particularbiological properties. Typical suitable auxiliaries are: extenders,solvents and carriers.

Suitable extenders are, for example, water, polar and nonpolar organicchemical liquids, for example from the classes of the aromatic andnonaromatic hydrocarbons (such as paraffins, alkylbenzenes,alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, ifappropriate, may also be substituted, etherified and/or esterified), theketones (such as acetone, cyclohexanone), esters (including fats andoils) and (poly)ethers, the unsubstituted and substituted amines,amides, lactams (such as N-alkylpyrrolidones) and lactones, thesulphones and sulphoxides (such as dimethyl sulphoxide).

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and also their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethyl sulphoxide, and also water.

According to the invention, “carrier” means a natural or synthetic,organic or inorganic substance which may be solid or liquid, with whichthe active ingredients are mixed or combined for better applicability,especially for application to plants or plant parts. The solid or liquidcarrier is generally inert and should be usable in agriculture.

Useful solid carriers are:

for example, ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as finely divided silica,alumina and silicates; suitable solid carriers for granules are: forexample, crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, and also synthetic granules of inorganicand organic meals, and granules of organic material such as paper,sawdust, coconut shells, maize cobs and tobacco stalks; suitableemulsifiers and/or foam-formers are: for example, nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates and also proteinhydrolysates; suitable dispersants are nonionic and/or ionic substances,for example from the classes of the alcohol-POE and/or -POP ethers, acidand/or POP-POE esters, alkylaryl and/or POP-POE ethers, fat- and/orPOP-POE adducts, POE- and/or POP-polyol derivatives, POE- and/orPOP-sorbitan- or -sugar adducts, alkyl or aryl sulphates, alkyl- orarylsulphonates and alkyl or aryl phosphates or the correspondingPO-ether adducts. Furthermore, suitable oligo- or polymers, for examplethose derived from vinylic monomers, from acrylic acid, from EO and/orPO alone or in combination with, for example, (poly)alcohols or(poly)amines. It is also possible to employ lignin and its sulphonicacid derivatives, unmodified and modified celluloses, aromatic and/oraliphatic sulphonic acids and their adducts with formaldehyde.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations.

It is possible to use dyes such as inorganic pigments, for example ironoxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Other possible additives are perfumes, mineral or vegetable, optionallymodified oils, waxes and nutrients (including trace nutrients), such assalts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Stabilizers, such as low-temperature stabilizers, preservatives,antioxidants, light stabilizers or other agents which improve chemicaland/or physical stability may also be present.

The formulations generally contain between 0.01 and 98% by weight ofactive ingredient, preferably between 0.5 and 90%.

The inventive active ingredient can be used in its commerciallyavailable formulations and in the use forms, prepared from theseformulations, as a mixture with other active ingredients, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances, herbicides,safeners, fertilizers or semiochemicals.

A mixture with other known active ingredients, such as herbicides,fertilizers, growth regulators, safeners, semiochemicals, or else withagents for improving the plant properties, is also possible.

When used as insecticides, the inventive active ingredients mayadditionally be present in their commercially available formulations andin the use forms, prepared from these formulations, as a mixture withsynergistic agents. Synergistic agents are compounds which increase theaction of the active ingredients, without it being necessary for thesynergistic agent added to be active itself.

When used as insecticides, the inventive active ingredients canfurthermore be present in their commercially available formulations andin the use forms, prepared from these formulations, as a mixture withinhibitors which reduce degradation of the active ingredient after usein the environment of the plant, on the surface of plants or in planttissues.

The active ingredient content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive ingredient concentration of the use forms can be from 0.00000001to 95% by weight of active ingredient, preferably between 0.00001 and 1%by weight.

The compounds are employed in a customary manner appropriate for the useforms.

The inventive active ingredients act not only against plant, hygiene andstored product pests, but also in the veterinary medicine sector againstanimal parasites (ecto- and endoparasites), such as hard ticks, softticks, mange mites, leaf mites, flies (biting and licking), parasiticfly larvae, lice, hair lice, feather lice and fleas. These parasitesinclude:

From the order of the Anoplurida, for example Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of the Acari (Acarina) and the orders of the Meta- andMesostigmata, for example. Argas spp., Ornithodorus spp., Otobius spp.,Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The inventive active ingredients of the formula (I) are also suitablefor controlling arthropods which infest agricultural productivelivestock, for example cattle, sheep, goats, horses, pigs, donkeys,camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees,other pets, for example dogs, cats, caged birds and aquarium fish, andalso so-called lest animals, for example hamsters, guinea pigs, rats andmice. By controlling these arthropods, cases of death and reductions inproductivity (for meat, milk, wool, hides, eggs, honey etc.) should bediminished, so that more economic and easier animal husbandry ispossible by use of the inventive active ingredients.

The inventive active ingredients are used in the veterinary sector andin animal husbandry in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, for example by injection (intramuscular,subcutaneous, intravenous, intraperitoneal and the like), implants, bynasal administration, by dermal use in the form, for example, of dippingor bathing, spraying, pouring on and spotting on, washing and powdering,and also with the aid of moulded articles containing the activeingredient, such as collars, ear marks, tail marks, limb bands, halters,marking devices and the like.

When used for cattle, poultry, pets and the like, the active ingredientsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activeingredients in an amount of 1 to 80% by weight, directly or after 100-to 10 000-fold dilution, or they can be used as a chemical bath.

It has additionally been found that the inventive compounds have astrong insecticidal action against insects which destroy industrialmaterials.

The following insects may be mentioned as examples and as preferred—butwithout any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendronspec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec. Dinoderus minutus;

Hymenopterons, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur;

Termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus;

Bristletails, such as Lepisma saccharina.

Industrial materials in the present connection should be understood tomean non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cardboards, leather, wood and processed wood productsand coating compositions.

The ready-to-use compositions may, if appropriate, comprise furtherinsecticides and, if appropriate, one or more fungicides.

With respect to possible additional additives, reference may be made tothe insecticides and fungicides mentioned above.

The inventive compounds can likewise be employed for protecting objectswhich come into contact with saltwater or brackish water, in particularhulls, screens, nets, buildings, moorings and signalling systems,against fouling.

Furthermore, the inventive compounds, alone or in combinations withother active ingredients, may be employed as antifouling agents.

In domestic, hygiene and store-product protection, the activeingredients are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaced for example dwellings, factory halls, offices, vehicle cabins andthe like. They can be employed alone or in combination with other activeingredients and auxiliaries in domestic insecticide products forcontrolling these pests. They are active against sensitive and resistantspecies and against all developmental stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleoptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of Diptera, for example, Aedes aegypti, Aedes albopictus,Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala,Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culextarsalis, Drosophila spp., Fannia canicularis, Musca domestica,Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxyscalcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix,Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active ingredients, such as phosphoricesters, carbamates, pyrethroids, neonicotinoids, growth regulators oractive ingredients from other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The inventive compounds of the formula (I) (active ingredients) havemarked herbicidal activity against a broad spectrum of economicallyimportant mono- and dicotyledonous annual harmful plants. Even perennialharmful plants which are difficult to control, which produce shoots fromrhizomes, rootstocks or other permanent organs, are well-controlled bythe active ingredients.

The application rate of active ingredient can vary within a relativelywide range. Essentially, it depends on the nature of the desired effect.In general, the application rates are between 1 g and 10 kg of activeingredient per hectare of soil area, preferably between 5 g and 5 kg perha.

The advantageous effect of the compatibility with crop plants of theinventive active ingredient combinations is particularly pronounced atcertain concentration ratios. However, the weight ratios of the activeingredients in the active ingredient combinations can be varied withinrelatively wide ranges. In general, from 0.001 to 1000 parts by weight,preferably from 0.01 to 100 parts by weight, particularly preferably0.05 to 20 parts by weight, of one of the compounds which improves cropplant compatibility (antidotes/safeners) mentioned above under (b′) arepresent per part by weight of active ingredient of the formula (I).

The inventive active ingredient combinations are generally applied inthe form of finished formulations. However, the active ingredientspresent in the active ingredient combinations can, as individualformulations, also be mixed during use, i.e. applied in the form of tankmixes.

For certain applications, in particular in the post-emergence method, itmay furthermore be advantageous to include, as further additives in theformulations, mineral or vegetable oils which are tolerated by plants(for example the commercial preparation “Rake Binol”), or ammoniumsalts, such as, for example, ammonium sulphate or ammonium thiocyanate.

The novel active ingredient combinations can be used as such, in theform of their formulations or the use forms prepared therefrom byfurther dilution, such as ready-to-use solutions, suspensions,emulsions, powders, pastes and granules. Application is in the customarymanner, for example by watering, spraying, atomizing, dusting orscattering.

The application rates of the active ingredient combinations according tothe invention can be varied within a certain range; they depend, interalia, on the weather and on soil factors. In general, the applicationrates are between 0.001 and 5 kg per ha, preferably between 0.005 and 2kg per ha, particularly preferably between 0.01 and 0.5 kg per ha.

Depending on their properties, the safeners for use in accordance withthe invention can be used to pretreat the seed of the crop plant (seeddressing) or can be introduced into the seed furrows prior to sowing orbe used separately prior to the herbicide or together with theherbicide, before or after emergence of the plants.

Examples of plants include important crop plants, such as cereals(wheat, barley, rice), maize, soya beans, potatoes, cotton, oilseedrape, beet, sugar cane and also fruit plants (with the fruits apples,pears, citrus fruits and grapevines), greater emphasis being given tocereals, maize, soya beans, potatoes, cotton and oilseed rape.

All plants and plant parts can be treated with the inventive activeingredients. In this context, plants should be understood to mean allplants and plant populations such as wanted and undesired wild plants orcrop plants (including naturally occurring crop plants). Crop plants canbe plants which can be obtained by conventional plant breeding andoptimization methods or by biotechnological and recombinant methods orby combinations of these methods, including the transgenic plants andinclusive of the plant cultivars protectable or not protectable by plantbreeders' rights. Plant parts should be understood to mean all parts andorgans of plants above and below the ground, such as shoot, leaf, flowerand root, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits and seed and roots, tubers andrhizomes. The plant parts also include harvested material, and alsovegetative and generative propagation material, for example cuttings,tubers, rhizomes, offshoots and seeds.

The inventive treatment of the plants and plant parts with the activeingredients is effected directly or by allowing the compounds to act ontheir surroundings, habitat or storage space by the customary treatmentmethods, for example by immersion, spraying, evaporation, fogging,broadcasting, painting on or injection and, in the case of propagationmaterial, especially in the case of seed, also by applying one or morecoats.

The present invention therefore also provides a method of controllingundesired plants or for regulating the growth of plants, preferably incrops of plants, wherein one or more inventive compound(s) is/areapplied to the plants (for example harmful plants such asmonocotyledonous or dicotyledonous weeds or undesired crop plants), tothe seeds (for example grains, seeds or vegetative propagules such astubers or shoot parts with buds) or to the area on which the plants grow(for example the area under cultivation). In this context, the inventivecompounds can be applied for example pre-planting (if appropriate alsoby incorporation into the soil), pre-emergence or post-emergence.Examples of individual representatives of the monocotyledonous anddicotyledonous weed flora which can be controlled by the inventivecompounds will be mentioned, though there is no intention to impose arestriction to particular species mentioned.

Monocotyledonous harmful plants of the genera: Aegilops, Agropyron,Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus,Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa,Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis,Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria,Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria,Scirpus, Setaria, Sorghum.

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia,Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella,Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura,Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium,Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria,Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago,Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex,Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,Xanthium.

The plants listed can be treated in accordance with the invention in aparticularly advantageous manner with the compounds of the generalformula I or the inventive active ingredient mixtures. The preferredranges stated above for the active ingredients or mixtures also apply tothe treatment of these plants. Particular emphasis is given to thetreatment of plants with the compounds or mixtures specificallymentioned in the present text.

If the inventive compounds are applied to the soil surface beforegermination, either the emergence of the weed seedlings is preventedcompletely or the weeds grow until they have reached the cotyledonstage, but then stop their growth and, finally, die completely afterthree to four weeks have elapsed.

When the active ingredients are applied post-emergence to the greenplant parts, growth stops after the treatment, and the harmful plantsremain in the growth stage of the time of application or die fully aftera certain period of time, so that competition by weeds, which is harmfulto the crop plants, is thus eliminated at an early point in time and ina sustained manner.

Although the inventive compounds display an outstanding herbicidalactivity against monocotyledonous and dicotyledonous weeds, crop plantsof economically important crops, for example dicotyledonous crops of thegenera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus,Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus,Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous cropsof the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum,Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, are damaged onlyto an insignificant extent, or not at all, depending on the structure ofthe respective inventive compound and its application rate. This is whythe present compounds are highly suitable for the selective control ofundesired vegetation in plant crops such as agriculturally useful plantsor ornamentals.

Moreover, the inventive compounds (depending on their respectivestructure and the application rate applied) have outstandinggrowth-regulatory properties in crop plants. They engage in the plantmetabolism in a regulatory fashion and can therefore be employed for theinfluencing, in a targeted manner, of plant constituents and forfacilitating harvesting, such as, for example, by triggering desiccationand stunted growth. Moreover, they are also suitable for generallycontrolling and inhibiting undesired vegetative growth withoutdestroying the plants in the process. Inhibiting the vegetative growthplays an important role in many monocotyledonous and dicotyledonouscrops since for example lodging can be reduced, or prevented completely,hereby.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andparts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineeringmethods, if appropriate in combination with conventional methods(Genetically Modified Organisms), and parts thereof are treated. Theterms “parts”, “parts of plants” and “plant parts” have been explainedabove.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated in accordance with theinvention. Plant cultivars should be understood to mean plants havingnovel properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. These can becultivars, bio- or genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, higher quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possible,which exceed the effects which were actually to be expected.

Owing to their herbicidal and plant-growth-regulatory properties, theactive ingredients can also be employed for controlling harmful plantsin crops of known genetically modified plants or genetically modifiedplants which are yet to be developed. As a rule, the transgenic plantsare distinguished by especially advantageous properties, for example byresistances to certain pesticides, mainly certain herbicides,resistances to plant diseases or causative organisms of plant diseases,such as certain insects, nematodes or microorganisms such as fungi,bacteria or viruses. Other special properties relate for example to theharvested material with regard to quantity, quality, storability,composition and specific constituents. Thus, transgenic plants with anincreased starch content or a modified starch quality or those with adifferent fatty acid composition of the harvested material are known.Further particular properties may be tolerance or resistance to abioticstresses, for example heat, cold, drought, salt and ultravioletradiation. The active ingredients can also be used in transgenic plantswhich are notable for higher yields, for example for improvedphotosynthesis performance or improved nutrient uptake.

It is preferred to use the inventive compounds of the formula (I) orsalts thereof in economically important transgenic crops of usefulplants and ornamentals, for example of cereals such as wheat, barley,rye, oats, sorghum and millet, rice, cassava and maize or else crops ofsugar beet, cotton, soya bean, oilseed rape, potato, tomato, peas andother vegetables.

It is preferred to employ the compounds of the formula (I) as herbicidesin crops of useful plants which are resistant, or have been maderesistant by recombinant means, to the phytotoxic effects of theherbicides.

Conventional ways of generating novel plants which, in comparison withexisting plants, have modified properties are, for example, traditionalbreeding methods and the generation of mutants. Alternatively, novelplants with modified properties can be generated with the aid ofrecombinant methods (see, for example, EP 0221044, EP 0131624). Forexample, the following have been described in several cases:

-   -   recombinant modifications of crop plants for the purpose of        modifying the starch synthesized in the plants (for example WO        92/011376 A, WO 92/14827 A, WO 91/19806 A),    -   transgenic crop plants which are resistant to certain herbicides        of the glufosinate type (cf., for example, EP 0242236 A, EP        242246 A) or of the glyphosate type (WO 92/000377 A) or of the        sulphonylurea type (EP 0257993 A, U.S. Pat. No. 5,013,659), or        are resistant to combinations or mixtures of these herbicides by        virtue of “gene stacking”, such as transgenic crop plants, for        example maize or soya with the trade name or the designation        Optimum™ GAT™ (Glyphosate ALS Tolerant). Additionally described        have been transgenic plants which are resistant to synthetic        auxins (e.g. 2,4 D), HRAC mode of action Class O and        aryloxyphenoxy propionate (fops, HRAC, Class A) (DHT, Dow        Agroscience Herbicide Tolerance Trait)    -   transgenic crop plants, for example cotton which is capable of        producing Bacillus thuringiensis toxins (Bt toxins), which make        the plants resistant to certain pests (EP 0142924 A, EP 0193259        A),    -   transgenic crop plants with a modified fatty acid composition        (WO 91/13972 A),    -   genetically modified plants which have new insect resistances,        for example based on the expression of toxins from Photorhabdus,        Xenorhabdus symbionts from entomopathogenic nematodes and toxins        from spiders, scorpions, ants, parasitic wasps,    -   genetically modified crop plants with novel constituents or        secondary metabolites, for example novel phytoalexins, which        bring about an increased disease resistance (EP 309862 A,        EP0464461 A),    -   genetically modified plants with reduced photorespiration which        feature higher yields and higher stress tolerance (EP 0305398        A),    -   transgenic crop plants which produce pharmaceutically or        diagnostically important proteins (“molecular pharming”),    -   transgenic crop plants which are distinguished by higher yields        or better quality,    -   transgenic crop plants which are distinguished by increased        tolerances to abiotic and biotic stresses,    -   transgenic crop plants which are distinguished by a combination,        for example of the abovementioned novel properties (“gene        stacking”).

A large number of molecular biology techniques by means of which noveltransgenic plants with modified properties can be produced are known inprinciple; see, for example, I. Potrykus and G. Spangenberg (eds.) GeneTransfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin,Heidelberg, or Christou, “Trends in Plant Science” 1 (1996) 423-431).

To carry out such recombinant manipulations, it is possible to introducenucleic acid molecules into plasmids, which permit a mutagenesis orsequence modification by recombination of DMA sequences. For example,base substitutions can be carried out, part-sequences can be removed, ornatural or synthetic sequences may be added with the aid of standardmethods. To link the DNA fragments with one another, it is possible toadd adapters or linkers to the fragments; see, for example, Sambrook etal., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold SpringHarbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Geneund Klone”, VCH Weinheim 2nd ed., 1996

The generation of plant cells with a reduced activity for a gene productcan be achieved for example by the expression of at least onecorresponding antisense RNA, a sense RNA for achieving a cosuppressioneffect or by the expression of at least one correspondingly constructedribozyme, which specifically cleaves transcripts of the abovementionedgene product.

To this end, it is possible firstly to use DNA molecules which compriseall of the coding sequence of a gene product, including any flankingsequences which may be present, or else DNA molecules which onlycomprise parts of the coding sequence, it being necessary for theseparts to be long enough to bring about an antisense effect in the cells.It is also possible to use DNA sequences which have a high degree ofhomology with the coding sequences of a gene product, but which are notentirely identical.

When expressing nucleic acid molecules in plants, the proteinsynthesized may be localized in any compartment of the plant cell. Inorder to achieve localization in a particular compartment, however, itis possible for example to link the coding region to DNA sequences whichensure the localization in a specific compartment. Such sequences areknown to the skilled worker (see, for example, Braun et al., EMBO J. 11(1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988),846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acidmolecules can also be expressed in the organelles of the plant cells.

The transgenic plant cells can be regenerated by known techniques togive intact plants. In principle, the transgenic plants may be plants ofany plant species, that is to say both monocotyledonous anddicotyledonous plants.

Thus, transgenic plants can be obtained which feature modifiedproperties as the result of overexpression, suppression or inhibition ofhomologous (=natural) genes or gene sequences or expression ofheterologous (=foreign) genes or gene sequences.

It is preferred to employ the inventive compounds (I) in transgeniccrops which are resistant to growth regulators, for example, 2, 4 D,dicamba, or to herbicides which inhibit essential plant enzymes, forexample acetyl CoA carboxylases, acetolactate synthases (ALS), EPSPsynthases, glutamine synthases (GS) or hydroxyphenylpyruvatedioxygenases (HPPD), or to herbicides from the group of the FOPs,sulphonylureas, glyphosates, glufosinates or benzoylisoxazoles andanalogous active ingredients, or to any combinations of these activeingredients.

-   -   It is particularly preferred to employ the inventive compounds        in transgenic crop plants which are resistant to a combination        of glyphosates and glufosinates, glyphosates and sulphonylureas        or imidazolinones. It is very particularly preferred to employ        the inventive compounds in transgenic crop plants, for example        maize or soya, with the trade name or the designation Optimum™        GAT™ (Glyphosate ALS Tolerant). In addition, it is particularly        preferred to employ the inventive compounds in transgenic plants        which are resistant to synthetic auxins (e.g. 2,4 D) with “HRAC        mode of action Class O” and aryloxy-phenoxy propionate (fops)        with “HRAC mode of action Class A” (e.g. DHT, Dow Agroscience        Herbicide Tolerance Trait).

When the inventive active ingredients are used in transgenic crops,effects are frequently observed—in addition to the effects on harmfulplants which can be observed in other crops—which are specific for theapplication in the transgenic crop in question, for example a modifiedor specifically widened spectrum of weeds which can be controlled,modified application rates which may be employed for application,preferably good combinability with the herbicides to which thetransgenic crop is resistant, and an effect on growth and yield of thetransgenic crop plants.

The invention therefore also provides for the use of the inventivecompounds of the formula (I) as herbicides for controlling harmfulplants in transgenic crop plants.

The inventive compounds can be used in the form of wettable powders,emulsifiable concentrates, sprayable solutions, dusting products orgranules in the customary formulations. The invention therefore alsoprovides herbicidal and plant growth-regulating compositions whichcomprise the inventive compounds.

The inventive compounds can be formulated in various ways according towhich biological and/or physicochemical parameters are required.Possible formulations include, for example: wettable powders (WP),water-soluble powders (SP), water-soluble concentrates, emulsifiableconcentrates (EC), emulsions (EW) such as oil-in-water and water-in-oilemulsions, sprayable solutions, suspension concentrates (SC), oil- orwater-based dispersions, oil-miscible solutions, capsule suspensions(CS), dusting products (DP), seed-dressing products, granules forscattering and soil application, granules (GR) in the form ofmicrogranules, spray granules, coated granules and adsorption granules,water-dispersible granules (WG), water-soluble granules (SG), ULVformulations, microcapsules and waxes.

These individual formulation types are known in principle and aredescribed, for example, in: Winnacker-Küchler, “Chemische Technologie”[Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986;Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y.,1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd.London.

The necessary formulation assistants, such as inert materials,surfactants,, solvents and further additives, are likewise, known andare described, for example, in: Watkins, “Handbook of Insecticide DustDiluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v.Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley &Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y.1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt,“Grenzflächenaktive Äthylenoxidaddukte” [Interface-Active Ethylene OxideAdducts], Wiss. Verlagsgesell, Stuttgart 1976; Winnacker-Küchler,“Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed.1986.

Based on these formulations, it is also possible to prepare combinationswith other pesticidally active ingredients, such as, for example,insecticides, acaricides, berbicides, fungicides, and also withsafeners, fertilizers and/or growth regulators, for example in the formof a finished formulation or as a tank mix.

Wettable powders are preparations which can be dispersed uniformly inwater and, as well as the active ingredient, apart from a diluent orinert substance, also comprise surfactants of the ionic and/or nonionictype (wetting agents, dispersants), for example polyoxyethylatedalkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fattyamines, fatty alcohol polyglycol ether sulphates, alkanesulphonates,alkylbenzenesulphonates, sodium lignosulphonate, sodium2,2′-dinaphthylmethane-6,6′-disulphonate, sodiumdibutylnaphthalenesulphonate or else sodium oleylmethyltauride. Toprepared the wettable powders, the active herbicidal ingredients areground finely, for example in customary apparatus such as hammer mills,blower mills and air-jet mills and simultaneously or subsequently mixedwith the formulation assistants.

Emulsifiable concentrates are prepared by dissolving the activeingredient in an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene or else relatively high-boiling aromatics orhydrocarbons or mixtures of the organic solvents with addition of one ormore surfactants of the ionic and/or nonionic type (emulsifiers). Theemulsifiers used may, for example, be: calcium alkylarylsulphonates suchas calcium dodecylbenzenesulphonate, or nonionic emulsifiers such asfatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcoholpolyglycol ethers, propylene oxide-ethylene oxide condensation products,alkyl polyethers, sorbitan esters, for example sorbitan fatty acidesters, or polyoxyethylene sorbitan esters, for example polyoxyethylenesorbitan fatty acid esters.

Dusting products are obtained by grinding the active ingredient withfinely divided solid substances, for example talc, natural clays such askaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They may beprepared, for example, by wet grinding by means of commercial bead millsand optional addition of surfactants as have, for example, already beenlisted above for the other formulation types.

Emulsions, for example oil-in-water emulsions (EW), can be prepared, forexample, by means of stirrers, colloid mills and/or static mixers usingaqueous organic solvents and optionally surfactants, as have, forexample, already been listed above for the other formulation types.

Granules can be produced either by spraying the active ingredient ontoadsorptive granulated inert material or by applying active ingredientconcentrates by means of adhesives, for example polyvinyl alcohol,sodium polyacrylate or else mineral oils, onto the surface of carrierssuch as sand, kaolinites or of granulated inert material. It is alsopossible to granulate suitable active ingredients in the mannercustomary for the production of fertilizer granules—if desired in amixture with fertilizers.

Water-dispersible granules are prepared generally by the customaryprocesses such as spray-drying, fluidized bed granulation, pangranulation, mixing with high-speed mixers and extrusion without solidinert material.

For the preparation of pan, fluidized bed, extruder and spray granules,see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G.Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical andEngineering 1967, pages 147 ff; “Perry's Chemical Engineer's Handbook”,5th Ed., McGraw-Hill, New York 1973, pp 8-57.

For further details regarding the formulation of crop protectioncompositions, see, for example, G. C. Klingman. “Weed Control as aScience”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., BlackwellScientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations contain generally from 0.1 to 99% byweight, in particular from 0.1 to 95% by weight, of inventive compounds.

In wettable powders, the active ingredient concentration is, forexample, from about 10 to 90% by weight; the remainder to 100% by weightconsists of customary formulation constituents. In the case ofemulsifiable concentrates, the active ingredient concentration may befrom about 1 to 90% by weight, preferably from 5 to 80% by weight.Dust-type formulations contain from 1 to 30% by weight of activeingredient, preferably usually from 5 to 20% be weight of activeingredient; sprayable solutions contain from about 0.05 to 80% byweight, preferably from 2 to 50% by weight of active ingredient. Inwater-dispersible granules, the active ingredient content depends partlyon whether the active compound is present in solid or liquid form andwhich granulation assistants, fillers, etc. are used. In the granulesdispersible in water, the content of active ingredients is, for example,between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active ingredient formulations mentioned optionallycomprise the respective customary adhesives, wetting agents,dispersants, emulsifiers, penetrants, preservatives, antifreeze agentsand solvents, fillers, carriers and dyes, defoamers, evaporationinhibitors and agents which influence the pH and the viscosity.

The inventive treatment method is preferably used on geneticallymodified organisms, for example plants or plant parts.

Genetically modified plants, known as transgenic plants, are plants inwhich a heterologous gene has been integrated stably into the genome.

The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and which, when introduced inthe nuclear, chloroplastic or mitochondrial genome, gives thetransformed plant new or improved agronomic or other properties byexpressing a protein or polypeptide of interest or by downregulating orsilencing other gene(s) which are present in the plant (using forexample antisense technology, cosuppression technology or RNAinterference [RNAi] technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active ingredients and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf colour, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active ingredient combinationsaccording to formula (I) may also have a strengthening effect in plants.Accordingly, they are suitable for mobilizing the defence system of theplant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are understood as mean, in the presentcontext, also those substances or combinations of substances which arecapable of stimulating the defence system of plants in such a way that,when subsequently inoculated with unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses, the treated plants display a substantialdegree of resistance to these unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. In the present case, unwantedphytopathogenic fungi and/or microorganisms and/or viruses areunderstood to mean phytopathogenic fungi, bacteria and viruses. Thus,the substances according to the invention can be employed for protectingplants against attack by the abovementioned pathogens within a certainperiod of time after the treatment. The period of time within whichprotection is effected generally extends from 1 to 10 days, preferably 1to 7 days, after the treatment of the plants with the activeingredients.

Plants which are also preferably treated in accordance with theinvention are resistant to one or more biotic stress factors, i.e. saidplants have an improved defence against animal and microbial pests, suchas nematodes, insects, mites, phytopathogenic fungi, bacteria, virusesand/or viroids.

In addition to the aforementioned plants and plant varieties, it is alsopossible in accordance with the invention to treat those which areresistant to one or more abiotic stress factors.

Abiotic stress conditions may include, for example, drought, coldexposure, heat exposure, osmotic stress, waterlogging, increased soilsalinity, increased exposure to minerals, ozone conditions, strong lightconditions, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients or shade avoidance.

Plants and plant varieties which may also be treated in accordance withthe invention are those plants characterized by enhanced yieldcharacteristics. Enhanced yield in said plants can be the result of, forexample, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated in accordance with the invention are hybridplants that already express the characteristics of heterosis, or hybridvigour, which results in generally higher yield, vigour, health andresistance towards biotic and abiotic stress factors. Such plants aretypically made by crossing an inbred male-sterile parent line (thefemale parent) with another inbred male-fertile parent line (the maleparent). Hybrid seed is typically harvested from the male sterile plantsand sold to growers. Male sterile plants can sometimes (e.g. in corn) beproduced by detasseling (i.e. the mechanical removal of the malereproductive organs or male flowers) but, more typically, male sterilityis the result of genetic determinants in the plant genome. In that case,and especially when seed is the desired product to be harvested from thehybrid plants, it is typically useful to ensure that male fertility inthe hybrid plants, which contain the genetic determinants responsiblefor male sterility, is fully restored. This can be accomplished byensuring that the male parents have appropriate fertility restorer geneswhich are capable of restoring the male fertility in hybrid plants thatcontain the genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedfor Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such as abarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated in accordance with theinvention are herbicide-tolerant plants, i.e. plants made tolerant toone or more given herbicides. Such plants can be obtained either bygenetic transformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition. One such efficientdetoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase are described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme of prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Further herbicide-resistant plants are plants that are made tolerant toacetolactate synthase (ALS) inhibitors. Known ALS inhibitors include,for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Further herbicide-resistant plants are plants which have been renderedtolerant to ACCase inhibitors.

Further plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated in accordance with theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

The term “insect-resistant transgenic plant”, as used herein, includesany plant containing at least one transgene comprising a coding sequenceencoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis        or an insecticidal portion thereof, such as the insecticidal        crystal proteins listed online at:        http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or        insecticidal portions thereof, e.g. proteins of the Cry protein        classes Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry3Ae, or Cry3Bb or        insecticidal portions thereof; or    -   2) a crystal protein from Bacillus thuringiensis or a portion        thereof which is insecticidal in the presence of a second other        crystal protein from Bacillus thuringiensis or a portion        thereof, such as the binary toxin made up of the Cy34 and Cy35        crystal proteins; or    -   3) a hybrid insecticidal protein comprising parts of two        different insecticidal crystal proteins from Bacillus        thuringiensis, such as a hybrid of the proteins of 1) above or a        hybrid of the proteins of 2) above, e.g. the Cry1A.105 protein        produced by corn event MON98034 (WO 2007/027777); or    -   4) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes induced into the        encoding DNA during cloning or transformation, such as the        Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A        protein in corn event MIR 604;    -   5) an insecticidal secreted protein from Bacillus thuringiensis        or Bacillus cereus, or an insecticidal portion thereof, such as        the vegetative insecticidal proteins (VIP) listed at:        http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html,        e.g. proteins from the VIP3Aa protein class; or    -   6) a secreted protein from Bacillus thruingiensis or Bacillus        cereus which is insecticidal in the presence of a second        secreted protein from Bacillus thuringiensis or B. cereus, such        as the binary toxin made up of the VIP1A and VIP2A proteins; or    -   7) a hybrid insecticidal protein comprising parts from different        secreted proteins from Bacillus thuringiensis or Bacillus        cereus, such as a hybrid of the proteins in 1) above or a hybrid        of the proteins in 2) above; or    -   8) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes induced into the        encoding DNA during cloning or transformation (while still        encoding an insecticidal protein), such as the VIP3Aa protein in        cotton event COT 102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated in accordance with theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   -   a. plants which contain a transgene capable of reducing the        expression and/or the activity of the poly(ADP-ribose)polymerase        (PARP) gene in the plant cells or plants.    -   b. plants which contain a stress tolerance-enhancing transgene        capable of reducing the expression and/or the activity of the        PARG-encoding genes of the plants or plant cells;    -   c. plants which contain a stress tolerance-enhancing transgene        coding for a plant-functional enzyme of the nicotinamide adenine        dinucleotide salvage biosynthesis pathway, including        nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic        acid mononucleotide adenyltransferase, nicotinamide adenine        dinucleotide synthetase or nicotinamide        phosphoribosyltransferase.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may likewise be treated in accordance withthe invention have an altered quantity, quality and/or storage stabilityof the harvested product and/or altered properties of specificingredients of the harvested product, for example:

-   -   1) transgenic plants which synthesize a modified starch whose        physiochemical characteristics, in particular the amylose        content or the amylose/amylopectin ratio, the degree of        branching, the average chain length, the side chain        distribution, the viscosity behaviour, the gelling strength, the        starch grain size and/or the starch grain morphology, is altered        compared to the synthesized starch in wild type plant cells or        plants, such that this modified starch is better suited for        certain applications.    -   2) transgenic plants which synthesize non-starch carbohydrate        polymers or which synthesize non-starch carbohydrate polymers        with altered properties in comparison to wild type plants        without genetic modification. Examples are plants which produce        polyfructose, especially of the inulin and levan type plants,        which produce alpha-1,4-glucans, plants which produce alpha-1,6        branched alpha-1,4-glucans, and plants producing alternan.    -   3) transgenic plants which produce hyaluronan.

Plants or plant cultivars (which can be obtained by plant biotechnologymethods such as genetic engineering) which may likewise be treated inaccordance with the invention are plants, such as cotton plants, withaltered fibre characteristics. Such plants can be obtained by genetictransformation, or by selection of plants containing a mutationimparting such altered fibre characteristics and include:

-   -   a) plants, such as cotton plants, which contain an altered form        of cellulose synthase genes;    -   b) plants, such as cotton plants, which contain an altered form        of rsw2 or rsw3 homologous nucleic acids;    -   c) plants, such as cotton plants, with an increased expression        of sucrose phosphate synthase;    -   d) plants, such as cotton plants, with an increased expression        of sucrose synthase;    -   e) plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fibre cell is altered,        for example through downregulation of fibre-selective        β-1,3-glucanase;    -   f) plants, such as cotton plants, which have fibres with altered        reactivity, for example through the expression of the        N-acetylglucosaminetransferase gene including nodC and chitin        synthase genes.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which my also be treated inaccordance with the invention are plants, such as oilseed rape orrelated Brassica plants, with altered oil profile characteristics. Suchplants can be obtained by genetic transformation or by selection ofplants containing a mutation imparting such altered oil characteristicsand include:

-   -   a) plants, such as oilseed rape plants, which produce oil having        a high oleic acid content;    -   b) plants, such as oilseed rape plants, which produce oil having        a low linolenic acid content;    -   c) plants, such as oilseed rape plants, which produce oil having        a low level of saturated fatty acids.

Particularly useful transgenic plants which may be treated in accordancewith the invention are plants which comprise one or more genes whichencode one or more toxins, are the following which are sold under thetrade names: YIELD GARD® (for example maize, cotton, soya beans),KnockOut® (for example maize), BiteGard® (for example maize), Bt-Xtra®(for example maize), StarLink® (for example maize), Bollgard® (cotton),Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example maize),Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plantswhich may be mentioned are maize varieties, cotton varieties and soyabean varieties which are sold under the trade names: Roundup Ready®(tolerance to glyphosate, for example maize, cotton, soya beans),Liberty Link® (tolerance to phosphinothricin, for example oilseed rape),IMI® (tolerance to imidazolinone) and SCS® (tolerance to sulphonylurea,for example maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize).

Particularly useful transgenic plants which may be treated in accordancewith the invention are plants containing transformation events, or acombination of transformation events that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://agbios.com/dbase.php).

The term “active ingredients” or “compounds” always also includes theactive ingredient combinations mentioned here too.

PREPARATION EXAMPLES Example (I-1-a-1)

Method A

0.41 g (0.58 mmol) of the compound according to example II-1-a-1 in asolution of 2 ml of DMF is added dropwise at room temperature within 30min to a solution of 5 ml of DMF and 164 mg (2.5 eq) of potassiumt-butoxide, and stirred at this temperature for 18 h. The mixture isadjusted to pH=1 with 1N hydrochloric acid and the residue obtained isfiltered off. Column chromatography purification (RP-silica gel,acetonitrile/water gradient) gives the inventive product (I-1-a-1)=200mg (38% of theory).

¹H NMR (400 MHz, d₆-DMSO): δ=6.75 (s, 2H, Ar—H), 4.70 (q, 2H, CH ₂—CF₃),3.57 (m, 1H, CH—OCH₂), 3.45 (m, 2H, OCH₂CH₃), 2.08 (d, 3H, Ar CH₃), 1.98(m), 1.70 (m), 1.29 (m, together 8 H, cyclohexyl), 1.10 (t, 3H, CH₃)ppm.

Example I-1-a-2

Method S

0.5 g (1.55 mmol) of the compound (I-1-a-1′) (known in generic termsfrom WO 97/02243) is admixed with 0.348 g (2 eq) of potassium t-butoxideand dissolved in 5 ml of DMA (solution 1). In addition, 0.296 g (1 eq)of copper(I) iodide and 1.35 g (6.7 eq) of 2,2,2-trifluoroethanol in 5ml of DMA (dimethylacetamide) are suspended under inert gas and admixedwith 1.17 g (6.7 eq) of potassium t-butoxide. After the exothermicreaction has ended, the mixture is admixed with solution 1 and stirredunder microwave irradiation at 145° C. for 2 h. The reaction mixture isfreed of the solvent under reduced pressure and admixed with 200 ml ofwater, and the remaining residue is removed and discarded. The aqueousphase is adjusted to pH 1 with 1N hydrochloric acid and the residueformed is filtered off. Column chromatography purification (RP-silicagel, water/acetonitrile gradient) gives 0.13 g=24% of theory ofinventive compound I-1-a-2 with an m.p. of 202-205° C.

In analogy to example (I-1-a-1) and example (I-1-a-2), and according tothe general information regarding preparation, the following compoundsof the formula (I-1-a) are obtained:

(I-1-a)

Ex. No. W X Y Z J¹ J² J³ D A B Analysis Isomer I-1-a-3 CH₃ C₂H₅ H 4- F FF H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H, cisCH₂—CF₃), 3.23 (m, 1H, CH—OCH₃) I-1-a-4 C₂H₅ C₂H₅ H 4- F F F H—(CH₂)₂—CH(OCH₃)—(CH₂)₂— 1H-NMR (400 MHz, CDCl₃): 4.47 (q, 2H, cisCH₂—CF₃), 3.29 (m, 1H, CH—OCH₃) I-1-a-5 CH₃ C₂H₅ H 4- F F F H—(CH₂)₂—CH(OCH₂CH₃)—(CH₂)₃— 1H-NMR (400 MHz, CDCl₃): 4.32 (q, 2H, transCH₂—CF₃), 3.86 (m, 1H, CH—OCH₂) I-1-a-6 CH₃ C₂H₅ H 4- F F F H—(CH₂)₂—C(—OCH₂—CH₂O—)—(CH₂)₂— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H,CH₂—CF₃), 3.96 (m, 4H, OCH₂CH₂O) I-1-a-7 CH₃ C₂H₅ H 4- F F F H—(CH₂)₂—C(—OCH₂—CH(CH₃)—O—)—CH₂)₂— 1H-NMR (400 MHz, CDCl₃): 4.33 (q, 2H,CH₂—CF₃), 1.27 (dd, 3H, OCHCH₃) I-1-a-8 CH₃ C₂H₅ H 4- F F F H—(CH₂)₂—CH(CH₃)—(CH₂)₂— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H, CH₂—CF₃),0.97 (d, 3H, CH—CH₃) I-1-a-9 C₂H₅ C₂H₅ H 4- F F F H CH₃ CH₃ 1H-NMR (400MHz, d₆-DMSO): 3.43 (m, 4H, CH₂—O and CH₂—CF₃) I-1-a-10 CH₃ C₂H₅ H 4- FF F H —(CH₂)₂—C(—O—CH(CH₃)—CH₂—CH(CH₃)—O—)—(CH₂)₂— 1H-NMR (400 MHz,CDCl₃): 4.33 (q, 2H, CH₂—CF₃), 4.08 and 3.93 (each m, each 1H, OCHCH₃I-1-a-11 CH₃ C₂H₅ H 4- F F F H C₂H₅ CH₃ 1H-NMR (400 MHz, CDCl₃): 4.34(q, 2H, CH₂—CF₃), 0.90 (t, 3H CH₂—CH₃) I-1-a-12 CH₃ C₂H₅ H 4- F F F H—CH₂—CH(CH₂—OCH₃)—(CH₂)₃— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H,trans:cis approx. 4:1 CH₂—CF₃), 3.26 (m, CH₂—O—CH₃) I-1-a-13 CH₃ C₂H₅ H4- F F F H —CH₂—CH(OCH₃)—(CH₂)₃— 1H-NMR (400 MHz, CDCl₃): 4.33 (q, 2H,trans CH₂—CF₃), 3.73 (m, CH—O—CH₃) I-1-a-14 CH₃ C₂H₅ H 4- F F F H—CH₂—CH(OC₃H₇)—(CH₂)₃— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H, transCH₂—CF₃), 3.86 (m, CH—O—CH₂) I-1-a-15 CH₃ C₂H₅ H 4- F F F H—CH₂—CH(OC₄H₉)—(CH₂)₃— 1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H, transCH₂—CF₃), 3.86 (m, CH—O—CH₂) I-1-a-16 CH₃ C₂H₅ H 4- F F F H CH₃ CH₃1H-NMR (400 MHz, CDCl₃): 4.34 (q, 2H, CH₂—CF₃), 1.45 (d, 6H, C(CH₃)₂)I-1-a-17 CH₃ CH₃ H 4- F F F H —(CH₂)₂—CH(CH₂—OCH₃)—(CH₂)₂— 1H-NMR (400MHz, d₆-DMSO): 4.66 (q, β 2H, CH₂—CF₃), 3.14 (d, CH₂—O—CH₃) I-1-a-18 CH₃CH₃ H 4- F F F H —(CH₂)₂—CH(CH₃)—(CH₂)₂— 1H-NMR (400 MHz, d₆-DMSO): 4.68(q, β 2H, CH₂—CF₃), 0.91 (d, CH—CH₃) I-1-a-19 CH₃ CH₃ H 4- F F F H—CH₂—CH(OC₃H₇)—(CH₂)₃— 1H-NMR (400 MHz, d₆-DMSO): 4.65 (q, trans 2H,CH₂—CF₃), 3.33 (m, CH—O—CH₂) I-1-a-20 CH₃ CH₃ H 4- F F F —(CH₂)₄— H1H-NMR (400 MHz, d₆-DMSO): 4.68 (q, 2H, CH₂—CF₃), 4.05 (m, CH—N)I-1-a-21 CH₃ C₂H₅ H 4- F F F —(CH₂)₃— H 1H-NMR (400 MHz, d₆-DMSO): 4.68(q, 2H, CH₂—CF₃), 4.15 (m, CH—N) I-1-a-22 CH₃ C₂H₅ H 4- F F F —(CH₂)₄— H1H-NMR (400 MHz, d₆-DMSO): 4.68 (q, 2H, CH₂—CF₃), 4.05 (m, CH—N)I-1-a-23 H C₂H₅ H 4- F F F H —(CH₂)₂—CHOCH₃—(CH₂)₂— 1H-NMR (300 MHz,CDCl₃): 4.34 (q, 2H, β O—CH₂—CF₃3), 3.16 (m, 1H, CH—O—CH₃) I-1-a-24 C₂H₅Cl H 4- F F F H —CH₂—CH(OC₄H₉)—(CH₂)₃— trans I-1-a-25 CH₃ CH₃ H 4- F F FH —(CH₂)₂—CH(OCH₃)—(CH₂)₂— 1H-NMR (400 MHz, d₆-DMSO): 1.43- cis 1.60 (m,4H, CH₂), 1.88-2.00 (m, 4H, CH₂), 2.06 (s, 6H, 2xAr—CH₃), 3.27 (s, 3H,OCH₃), 4.61-4.66 (q, 2H, OCH₃CF₃), 6.73 (s, 2H, ArH) I-1-a-26 CH₃ CH₃ H4- F F F H —(CH₂)₂—O—(CH₂)₂— 1H-NMR (400 MHz, d₆-DMSO): 1.27- — 1.30(2m, 2H, CH₂), 2.07 (s, 6H, 2xAr—CH₃), 3.67-3.73 (zt, 2H, OCH₂),3.82-3.87 (m, 2H, OCH₂), 4.62-4.69 (q, 2H, OCH₂CF₃), 6.74 (s, 2H, ArH)I-1-a-27 H CH₃ H 5- F F F H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— 1H-NMR (400 MHz,d₆-DMSO): 1.97 (s, cis 3H, Ar—CH₃), 3.27 (s, 3H, OCH₃), 4.59- 4.66 (m,2H, CH₂CF₃), 6.75 (d, 1H, ArH), 6.86-6.89 (m, 1H, ArH), 7.13 (d, 1H,ArH) I-1-a-28 CH₃ CH₃ H 3- F F F H —(CH₂)₂—CH(OC₂H₅)—(CH₂)₂— 1H-NMR (400MHz, d₆-DMSO): 1.11 (t, cis/trans approx. 10:1 3H, CH₃—CH₂O), 1.97, 2.03(2s, each 3H, ArCH₃), 3.47-3.52 (q, 2H, O—CH₂CH₃), 4.58-4.65 (q, 2H,O—CH₂CF₃), 6.92 (d, 1H, ArH), 6.99 (d, 1H, ArH) I-1-a-29 CH₃ CH₃ H 3- FF F H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— 1H-NMR (400 MHz, d₆-DMSO): 1.97, cis 2.03(2s, each 3H, Ar—CH₃), 3.27 (s, 3H, OCH₃), 4.58-4.65 (m, 2H, O—CH₂CF₃),6.90 (d, 1H, ArH), 6.99 (d, 1H, ArH) Ex. No. W X Y Z J¹ J² J³ D A B M.p.° C./Analysis Isomer I-1-a-30 H CH₃ H 5- F F F H —(CH₂)₂—O—(CH₂)₂—1H-NMR (400 MHz, d₆-DMSO): 3.59- — 3.69 (m, 2H, OCH₂), 3.81-3.85 (m, 2H,OCH₂), 4.54-4.61 (m, 2H, O—CH₂CF₃), 6.74-6.76 (m, 1H, ArH), 6.82-6.83(d, 1H, ArH), 7.04-7.06 (d, 1H, ArH) I-1-a-31 CH₃ CH₃ 3- F F F H—(CH₂)₂—O—(CH₂)₂— 1H-NMR (400 MHz, d₆-DMSO): 1.28- — 1.33 (m, 2H,CH₂—CH₂—O), 1.98, 2.04 (2s, each 3H, ArCH₃), 3.67-3.74 (m, 2H, O—CH₂),3.48-3.88 (m, 2H, O—CH₂), 4.59- 4.65 (m, 2H) O—CH₂CF₃) I-1-a-32 CH₃ CH₃H 4- F F F H

269 Mixture I-1-a-33 CH₃ CH₃ H 4- F F F H

190-193 cis I-1-a-34 CH₃ CH₃ H 4- F F F H

 94-100 trans I-1-a-35 CH₃ C₂H₅ H 4- F F F H

d) trans I-1-a-36 CH₃ CH₃ H 4- F F F H

a) trans I-1-a-37 CH₃ C₂H₅ H 4- F F F H

196 cis I-1-a-38 CH₃ C₂H₅ H 4- F F F H

189 trans I-1-a-39 CH₃ CH₃ H 4- F F F H

258-264 Mixture β I-1-a-40 CH₃ C₂H₅ H 4- F F F H

236 Mixture β I-1-a-41 CH₃ C₂H₅ H 4- F F F H

e) cis I-1-a-42 H CH₃ H 4- F F F H —(CH₂)₂—CHOCH₃—(CH₂)₂ 101-102 cisI-1-a-43 CH₃ CH₃ H 3- F F F H

139 trans I-1-a-44 H CH₃ H 5- F F F H

b) cis I-1-a-45 H CH₃ H 5- F F F H

c) trans I-1-a-46 CH₃ C₂H₅ H 4- F F F —CH₂—C(—O—CH₂—CH₂—O—)—CH₂— H201-204 a) 1H NMR (400 MHz, d₆-DMSO): δ = 1.09 (s, 3H, CH₃), 1.12-1.15(dm, 2H, CH₂), 1-61-1.69 (tm, 2H, CH₂), 1.74-1.78 (dm, 2H, CH₃), 2.06(s, 6H, ArCH₃), 3.11 (s, 3H, OCH₃), 4.61-4.68 (q, 2H, OCH₂CF₃), 6.73 (s,2H, ArH), 7.81 (br, 1H, NH) ppm b) 1H NMR (600 MHz, d₆-DMSO): δ = 1.12(t, 3H, CH₂CH₃), 1.43-1.64 (3m, 3H), 2.21-2.25 (m, 1H), 2.34-2.36 (cm,1H), 3.32-3.45 (2m, 4H, OCH₂—CH₃, O—CH₂), 4.66-4.70 (q, 2H, OCH₂CF₃),6.75 (d, 1H, ArH), 6.88-6.90 (m, 1H, ArH), 7.14-7.15 (d, 1H, ArH), 7.79(sbr, 1H, NH) c) 1H NMR (400 MHz, d₆-DMSO): δ = 1.11 (t, 3H, CH₂—CH₃),1.47-1.49 (m, 1H), 1.59-1.68 (m, 1H), 2.09 (s, 3H, Ar—CH₃), 3.32-3.36(cm, 2H, OCH₂), 3.41-3.47 (q, 2H, OCH₂—CH₃), 4.59-4.66 (q, 2H,O—CH₂—CF₃), 6.75 (d, 1H, ArH), 6.86-6.89 (m, 1H, ArH), 7.12-7.14 (d, 1H,ArH), 7.69 (s, br, 1H, NH) d) 1H NMR (400 MHz, CDCl₃): δ = 3.42 (dd, 2H,OCH₃), 4.32 (m, 2H, OCH₂CF₃) e) 1H NMR (400 MHz, CDCl₃): δ = 3.52 (dd,2H, OCH₃), 4.32 (m, 2H, OCH₃CF₃)

Example (I-1-b-1)

0.15 g (0.36 mmol) of the compound according to example (I-1-a-3) isinitially charged with 0.44 g (1.2 eq) of triethylamine and 1.5 mg ofDMAP in 8 ml of EtOAc¹⁾, and the mixture is stirred at 50° C. for 10min. Subsequently 0.043 g (1.1 eq) of isobutyryl chloride in 2 ml ofEtOAc¹⁾ is added dropwise over 20 min and then the mixture is left tostir at 50° C. for 6 h and then at RT overnight. The mixture is admixedwith 10 ml of sodium hydrogencarbonate solution, the organic phase isremoved, the aqueous phase is reextracted with 20 ml of EtOAc¹⁾, and thecombined organic phases are dried over sodium sulphate. The residuewhich remains after the concentration is taken up in a mixture ofEtOAc¹⁾ and n-heptane, and filtered again. This gives 0.07 g ofinventive compound (I-1-b-1)=40% of theory.

¹H NMR (400 MHz, CDCl₃): δ=6.61 (pseudo d, 2H, Aryl-H), 6.37 (s, 1H,NH), 4.35 (q, 2H, CH ₂—CF₃), 3.37 (s, 3H, OCH₃), 3.24 (m, 1H, CH—OCH₃),2.51 (m, 3H, CH₂—Ar and CH(CH₃)₂), 2.20. (s, 3H, ArylCH₃), 2.19, 1.79,1.38 (each m, together 8 H cyclohexyl), 1.13 (t, 3H, Aryl CH₂CH₃), 1.00(dd, 6H, (CH₃)₂) ppm. Ethyl acetate

In analogy to example (I-1-b-1), example (I-1-b-2) is obtained.

Example (I-1-c-1)

0.15 g (0.36 mmol) of the compound according to example (I-1-a-3) isinitially charged with 0.44 g (1.2 eq) of triethylamine in 8 ml ofdichloromethane and stirred at RT for 5 min. Subsequently, 0.043 g (1.1eq) of ethyl chloroformate is added dropwise over 20 min and then themixture is left to stir at RT overnight. It is admixed with 5 ml of 10%sodium carbonate solution, and the organic phase is removed and dried.The residue which remained after the concentration was purified bycolumn chromatography (silica gel, EtOAc¹⁾/n-heptane gradient). Thisgive 0.12 g=68% of theory of inventive compound (I-1-c-1).

¹H NMR (400 MHz, CDCl₃): δ=6.66 (pseudo d, 2H, Aryl-H), 6.37 (s, 1H,NH), 4.34 (q, 2H, CH ₂—CF₃), 4.01 (q, 2H, OCH₂CH₃), 3.40 (s, 3H, OCH₃),3.25 (m, 1H, CH—OCH₃), 2.49 (m, 2H, CH₂—Ar), 2.21 (s, 3H, ArylCH₃),2.22, 1.96, 1.75, 1.40 (each m, together 8 H cyclohexyl), 1.13 (m, 6H,aryl CH₂CH₃ and OCH₂CH₃) ppm.

In analogy to example (I-1-c-1), and according to the generalinformation regarding preparation, the following compounds of theformula (I-1-c) are obtained:

(I-1-c)

Ex. Iso- No. W X Y Z J¹ J² J³ D A B L M R² Analysis mer I-1- CH₃ CH₃ H4- F F F H —CH₂—CH(OC₂H₅)—(CH₂)₃— O O C₂H₅ ¹H NMR 400 MHz, CDCl₃): 4.34trans c-2 (q, 2H, CH₂—CF₃), 4.01 (q, 2H, OCH₂), 3.42 (m, 3H, CH—OCH₂)I-1- CH₃ CH₃ H 4- F F F H —CH₂—CH(OC₄H₉)—(CH₂)₃— O O C₂H₅ trans c-3 I-1-C₂H₅ C₂H₅ H 4- F F F H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— O O C₂H₅ ¹H NMR (400MHz, CDCl₃), 4.33 cis c-4 (q, 2H, CH₂—CF₃), 4,01 (q, 2H, OCH₂), 3.22 (m,1H, CH—OCH₃) I-1- CH₃ C₂H₅ H 4- F F F H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— O OC₂H₅ ¹H NMR (400 MHz, CDCl₃), 4.16 cis c-5 (dt, 2H, CH₂—CHF₂), 4,03 (q,2H, OCH₂), 3.23 (m, 1H, CH—OCH₃) I-1- CH₃ CH₃ H 3- F F F H—(CH₂)₂—CH(OC₂H₅)—(CH₂)₂— O O C₂H₅ ¹H NMR (400 MHz, d₆-DMSO): cis c-60.99, 1.11 (2t, each 2H, O—CH₂— CH₃) 1.98, 2.05 (2s, each 3H, ArCH₃),3.29 (zm, 1H, CHOC₂H₅), 3.46-3.52 (q, 2H, CHO—CH₂CH₃), 3.94-3.99 (q, 2H,OCH₂CH₃), 4.61- 4.67 (m, 2H, OCH₂CF₃) I-1- CH₃ C₂H₅ H 4- F F F—CH₂C(—O—CH₂—CH₂—O—)— H O O C₂H₅ ¹H NMR (400 MHz, CDCl₃), 6.70 c-7 CH₂—and 6.66 (each s, 1H, Ar—H), 4.89 (s, 1H, CH—N), 4.32 (dt, 2H, CH₂—CF₃),4.17 (q, 2H, OCH₃)

Example II-1

1.5 g (5.7 mmol) of the compound according to example (XXXI-1) areadmixed with 3.4 g (5 eq) of thionyl chloride and one drop of DMF. Themixture is heated to boiling under reflux until the evolution of gas hasended, then the reaction solution is concentrated and admixed with 4 mlof dichloromethane (solution 1). 1.5 g (1.1 eq) of methyltrans-3-ethoxy-1-aminocyclohexancarboxylate and 0.7 g (1.2 eq) oftriethylamine are dissolved in 50 ml of dichloromethane, and solution 1is added dropwise within 1 h. After stirring for 18 h, the mixture isadmixed with 10 ml of water, and the organic phase is removed,concentrated and purified by column chromatography. This gives 0.56 g(=23% of theory) of example II-a-1.

1H NMR (400 MHz, CDCl₃): δ=4.36 (q, 2H, CH₂—CF₃), 3.71 (s, 3H, OCH₃),3.40 (m, 2H, CH—OCH₂) ppm.

In analogy to example (II-1), and according to the general informationregarding preparation, the following compounds of the formula (II) areobtained:

(II)

Ex. Iso- No. W X Y Z J¹ J² J³ D A B R⁸ Analysis mer II-2 CH₃ CH₃ H 4- FF F H —CH₂CH(OC₄H₉)—(CH₂)₃— CH₃ ¹H NMR (400 MHz, trans CDCl₃): 4.34 (q,2H, CH₂—CF₃), 3.70 (s, 3H, OCH₃), 3.32 (m, 2H, CH—OCH₂) II-3 CH₃ CH₃ H4- F F F H —(CH₂)₂—CH(CH₂OCH₃)—(CH₂)₂— CH₃ ¹H NMR (300 MHz, β CDCl₃):4.34 (q, 2H, CH₂—CF₃), 3.70 (s, 3H, OCH₃), 3.11 (m, 2H, CH₂—OCH₂) II-4CH₃ CH₃ H 4- F F F H —(CH₂)₂—CH(OCH₃)—(CH₂)₂— CH₃ ¹H NMR (400 MHz, cisd₆-DMSO): 2.23 (s, 6H, Ar—CH₃), 3.23 (s, 3H, OCH₃), 3.50 (s, 2H, CH₂CO),3.52 (s, 3H, CO₂CH₃), 4.58-4.65 (q, 2H, O—CH₂CF₃), 6.69 (s, 2H, ArH)II-5 CH₃ CH₃ H 4- F F F H —(CH₂)₂—O—(CH₂)₂— CH₃ ¹H NMR (400 MHz, —d₆-DMSO): 1.84-1.97 (m, 4H, CH₂), 2.23 (s, 6H, Ar—CH₃), 3.51 (s, 2H,CO—CH₂), 3.55 (s, 3H, CO₂CH₃), 4.58-4.65 (q, 2H, ArH)

The following compounds of the formula (I-1′-a) which were used toprepare compounds of the formula (I-1-a) are novel and can be preparedaccording to method A:

(I-1′-a)

Ex. Iso- No. W X Y A B M.p. mer I-1′- C₂H₅ C₂H₅ H —(CH₂)₂—CHOCH₃—(CH₂)₂—225- cis a-1 228 I-1′- C₂H₅ C₂H₅ H —(CH₂)₂—O—(CH₂)₂— 278 — a-2

The phenylacetic acids of the formula (XXXI′) required to prepare thecompound (I-1′-a) are obtained, for example, by bromination in glacialacetic acid.

Example (XXXI′-1)

3.85 g (20 mmol) of 2,6-diethylphenylacetic acid are initially chargedin 40 ml of glacial acetic acid. At 10° C.-15° C., 3.2 g (20 mmol) ofbromine in 12 ml of glacial acetic acid are added dropwise withinapprox. 40 min. After approx. 2 hours, another 1.1 g of bromine in 4 mlof glacial acetic acid are added, and the mixture is stirred at roomtemperature overnight. After evaporating off the glacial acetic acidunder reduced pressure, the residue is taken up in 40 ml of 2N sodiumhydroxide solution and washed with MTB ether, and the aqueous phase isacidified, extracted with dichloromethane, dried and concentrated underreduced pressure.

This gives 4.3 g (72% of theory) of the compound (XXXI′-1).

¹H NMR (400 MHz, d₆-DMSO): δ=1.08, 1.12 (2t, each 3H, CH₂—CH ₃),2.54-2.60 (q, 2H, CH ₂CH₃), 2.76-2.81 (q, 2H, CH ₂CH₃), 3.70 (s, 2H, CH₂CO), 6.98, 7.41 (2d, each 1H, Ar—H) ppm.

Example (I-2-a-1)

1.36 g (34 mmol) of sodium hydride (60%) are initially charged in 30 mlof THF, and 3.10 g (31 mmol) of trifluoroethanol are added dropwise,after the evolution of gas has ended 6.48 g (34 mmol) of copper(I)iodide are added, a solution of 2.00 g (6.18 mmol) of (I-2-a-1′) (knownin generic terms from WO 98/05638) dissolved in 20 ml of THF is slowlyadded dropwise, and the mixture is boiled at reflux for 2.5 h.

For workup, the cooled mixture is admixed with water, acidified withdil. HCl and extracted by shaking with ether and ethyl acetate, and theorganic phase is dried, filtered and concentrated.

This gives 1.57 g (70% of theory) of example (I-2-a-1); logP (HCOOH)2.59.

1H NMR (CD₃CN): δ=1.80-2.20 (m, 8H), 2.15 (s,3H), 3.35 (m, 2H), 7.15 (m,1H), 7.30 (m, 1H), 7.35 (m, 1H) ppm.

Example (I-2-a-2)

0.294 g (2.62 mmol) of potassium tert-butoxide is initially charged in 7ml of DMF²⁾ and cooled to 0° C., a solution of 0.732 g (1.75 mmol) ofexample (III-1) in 3 ml of DMF²⁾ is added dropwise at 0-10° C., and themixture is stirred at room temperature overnight.

For workup, the DMF²⁾ is evaporated off by rotary evaporation, theresidue is stirred in water, the alkaline phase is extracted with methyltert-butyl ether, and the aqueous phase is acidified with hydrochloricacid, extracted with dichloromethane, dried, filtered and concentrated.The crude product is purified by means of chromatography on silica gel(eluent: ethyl acetate/cyclohexane). ²⁾ Dimethylformamide

0.416 g (57% of theory) of example (I-2-a-1), logP (HCOOH) 2.45.

1H NMR (d₆-DMSO): δ=1.50 (m, 2H), 2.10 (s, 6H), 2.20 (m, 2H), 3.65 (m,2H), 3.95 (m, 2H), 6.80 (s, 2H) ppm.

In analogy to examples (I-2-a-1) and (I-2-a-2), and according to thegeneral information regarding preparation, the following compounds ofthe formula (I-2-a) are obtained:

(I-2-a)

Ex. No. W X Y Z J¹ J² J³ A B Analysis Isomer I-2-a-3 H CH₃ H 3- F F F—(CH₂)₂—CHOCH₃—(CH₂)₂— a) cis I-2-a-4 H CH₃ H 3- F F F—(CH₂)₂—CHOCH₃—(CH₂)₂— b) trans I-2-a-5 CH₃ CH₃ H 4- F F F—(CH₂)₂—CHOCH₃—(CH₂)₂— c) cis I-2-a-6 CH₃ CH₃ H 4- F F F—(CH₂)₂—CHOCH₃—(CH₂)₂— d) trans a)1H NMR (d₆-DMSO): δ = 1.50 (m, 2H),1.65 (m, 2H), 2.05 (m, 4H), 2.10 (s, 3H), 3.25 (m, 1H), 3.30 (s, 3H),4.65 (m, 2H), 6.80 (m, 1H), 6.95 (m, 1H), 7.15 (m, 1H) ppm. b) 1H NMR(d₆-DMSO): δ = 1.40 (m, 2H), 1.70 (m, 2H), 1.95 (m, 2H), 2.10 (s, 3H),2.15 (m, 2H), 3.30 (s, 3H), 3.50 (m, 1H), 4.65 (m, 2H), 6.80 (m, 1H),7.15 (m, 1H), ppm. c) 1H NMR (d₆-DMSO): δ = 1.45 (m, 2H), 1.65 (m, 2H),2.00 (m, 4H), 2.05 (s, 3H), 3.20 (m, 1H), 3.28 (s, 3H), 4.65 (m, 2H),6.75 (m, 2H) ppm. d) 1H NMR (d₆-DMSO): δ = 1.41 (m, 2H), 1.75 (m, 2H),1.95 (m, 2H), 2.06 (s, 3H), 2.15 (m, 2H), 3.25 (s, 3H), 3.52 (m, 1H),4.65 (m, 2H), 6.75 (m, 2H), ppm.

Example (I-2-b-1)

56 mg (0.16 mmol) of example I-2-a-1 are initially charged in 10 ml ofdichloromethane, 18 mg (0.18 mmol) of triethylamine are added at roomtemperature, 21 mg (0.17 mmol) of pivaloyl chloride are added dropwiseat 0-10° C. and the mixture is stirred at room temperature for 1 h.

For workup, the mixture is extracted by shaking with dil. citric acidand 5% NaOH, and the organic phase is dried and concentrated.

This gives 61 mg (83% of theory) of example (I-2-b-1), logP (HCOOH)4.69.

1H NMR (D₆-DMSO): δ=1.10 (s, 9H), 1.80-2.20 (m, 8H), 2.15 (s, 3H), 4.65(m, 2H), 6.75 (m, 1H), 7.00 (m, 1H), 7.20 (m, 1H) ppm.

Example (III-1)

0.621 g (3.56 mmol) of ethyl 1-hydroxytetrahydropyrancarboxylate and1.00 g (3.56 mmol) of 2,6-dimethyl-4-trifluoroethoxyphenylacetylchloride are boiled under reflux in 20 ml of toluene for 12 h.

For workup, the toluene is evaporated off by rotary evaporation, theresidue is partitioned between methyl t-butyl ether and 5% sodiumhydroxide solution, and the organic phase is dried and concentrated.

This gives 0.732 g (47% of theory) of the compound (III-1), logP (HCOOH)3.78,

1H NMR (d₆-DMSO): δ=1.15 (m, 3H), 1.80-2.00 (m, 4H), 2.25 (s, 6H),3.40-3.70 (m, 4H), 4.05 (m, 2H), 4.65 (m, 2H), 6.75 (m, 2H) ppm.

Example I-6-a-1

300 mg (0.934 mmol) of the compound according to example (I-6′-a-1) aredissolved in 5 ml of collidine and admixed with 702 mg (6.26 mmol) ofpotassium tert-butoxide (solution 1). In a separate flask, 178 mg (0.934mmol) of copper(I) iodide, 841 mg (8.4 mmol) of trifluoroethanol and 210mg (1.87 mmol) of potassium tert-butoxide are dissolved in 5 ml ofcollidine. Solution 1 is added dropwise thereto, the vessel is rinsedwith 2 ml of DMF and the reaction mixture is stirred at 145° C. in amicrowave for 1 hour. The solvent is drawn off under reduced pressure,and the residue is taken up in water and filtered through Celite. 10 mlof ammonium chloride solution are added to the filtrate which isacidified with 2N hydrochloric acid. The solid which precipitates out isfiltered off with suction and dried.

Yield: 185 mg (58% of theory).

¹ H NMR, (400 MHz, CDCl₃): 1.38-1.48 (m, 1H), 1.70 (me, 3H), 20.05 and2.10 (each s, each 3H), 3.15 (me, 2H), 4.31 (q, 2H), 6.65 (s, 2H) ppm.

The compound of the formula (I-6′-a-1) which is used to prepare thecompound of the formula (I-6-a-1) is novel and can be prepared accordingto method F:

Example (I-6′-a-1)

¹H NMR (400 MHz, CDCl₃): 1.43 (mc, 1H), 1.68 (mc, 3H), 2.08 and 2.11(each s, each 3H), 2.98 and 3.28 (each mc, each 1H), 7.18 (s, 2H) ppm.

Example I-6-c-1

69 mg (0.2 mmol) of the compound according to example (I-6-a-1) aredissolved in 5 ml of dichloromethane and admixed with 24 mg (0.22 mmol)of ethyl chloroformate and 62 mg (0.6 mmol) of triethylamine. Themixture is left at room temperature for 30 minutes. It is concentratedand purified by means of preparative HPLC (RP-18, acetonitrile/watergradient (1% trifluoroacetic acid)).

Yield: 57 mg.

¹H NMR (400 MHz CDCl₃): 1.21 (t, 3H), 1.50 (mc, 1H), 1.65-1.88 (m, 3H),1.94 (mc, 1H), 2.06 and 2.09 (each s, each 3H), 3.11 and 3.80 (each mc,each 1H), 4.12 (mc, 2H), 4.30 (q, 2H), 6.62 (s, 2H) ppm.

Example I-8-a-1

0.3 g of8-(4-bromine-2,6-diethylphenyl)-9-hydroxy-1,2,4,5-tetrahydro-7H-pyrazolo[1,2-d][1,4,5]oxadiazepin-7-one(known from WO 99/047525 ex.: 1.087) is dissolved under a nitrogenatmosphere with 2 eq (0.176 g) of potassium t-butoxide in 5 ml ofcollidine (solution 1).

Subsequently, 150 mg of copper(I) iodide, 0.69 g of2,2,2-trifluoroethanol and 6.7 eq (0.591 g) of potassium t-butoxide aresuspended in 5 ml of collidine under a nitrogen atmosphere. Solution 1is added thereto and the mixture is left to stir at 145° C. for 1 hunder microwave conditions.

The solvent is removed under reduced pressure and the remaining residueis taken up in water. The remaining residue is filtered off and themother liquor is adjusted to pH=1 with 1N hydrochloric acid. Afterextracting with ethyl acetate and drying over sodium sulphate, themixture is concentrated to obtain 0.275 g of inventive compound I-8-a-1.

In analog to example (I-8-a-1), and according to the general informationregarding preparation, the following compounds of the formula (I-8-a)are obtained:

(I-8-a)

Ex. No. W X Y Z J¹ J² J³ A D Analysis I-8-a-1 C₂H₅ C₂H₅ H 4- F F F—(CH₂)₂—O—(CH₂)₂— ¹H NMR (400 MHz CDCl₃): 6.72 (m, 2H), Ar—H) 4.32 (m,2H, CF₃—CH₂), 3.75 (m, 2H, CH₂—N) I-8-a-2 C₂H₅ CH₃ H 4- F F F—(CH₂)₂—O—(CH₂)₂— ¹H NMR (400 MHz CDCl₃): 6.70 (d, 1H), Ar—H) 6.60 (d,1H, Ar—H), 4.32 (m, 2H, CF₃—CH₂), 3.80 (m, 2H, CH₂—N) I-8-a-3 CH₃ CH₃ H4- F F F —(CH₂)₂—O—(CH₂)₂— ¹H NMR (400 MHz CDCl₃): 6.72 (d, 1H), Ar—H)6.62 (d, 1H, Ar—H), 4.32 (m, 2H, CF₃—CH₂), 3.82 (m, 2H, CH₂—N) I-8-a-4C₂H₅ CH₃ H 4- F F F —(CH₂)₄— ¹H NMR (400 MHz CDCl₃): δ = 3.68 (m, 4H,CH₂N), 4.32 (m, 2H, OCH₂CF₃) I-8-a-5 C₂H₅ C₂H₅ H 4- F F F —(CH₂)₄— ¹HNMR (400 MHz CDCl₃): 6.68 (d, 2H, Ar— H), 4.33 (m, 2H, CF₃—CH₂), 3.62(m, 4H, CH₂—N) I-8-a-6 CH₃ CH₃ H 4- F F F —(CH₂)₄— ¹H NMR (400 MHzCDCl₃): 6.68 (d, 2H, Ar— H), 4.33 (m, 2H, CF₃—CH₂), 3.62 (m, 2H, CH₂—N)

Example I-8-b-1

0.05 g of the compound according to example I-8-a-4 is dissolved undernitrogen atmosphere in 1 ml of dichloromethane. Subsequently, 17 mg of2,2-dimethylpropanoyl chloride and 17 mg of triethylamine are added, andthe mixture is stirred at room temperature overnight. The mixture isadded to 5 ml of water and the phases are separated by means of anextraction cartridge. The organic phase is concentrated and then theresidue is purified by reverse phase HPL chromatography(acetonitrile/water gradient, 0.05% TFA). This gives 0.024 g ofinventive compound I-8-b-1.

¹H NMR (400 MHz, CDCl₃): 6.67 (s, 2H, Ar—H), 4.32 (q, 2H, OCH₂CF₃), 1.92(m, 4H, CH₂), 1.05 (s, 9H, t-Bu)

In analogy to example (I-8-b-1), and according to the generalinformation regarding preparation, the following compounds of theformula (I-8-b) are obtained:

(I-8-b)

Ex. No. W X Y Z J¹ J² J³ A D R¹ Analysis I-8-b-2 C₂H₅ C₂H₅ H 4- F F F—(CH₂)₂—O—(CH₂)₂— C(CH₃)₃ a) I-8-b-3 C₂H₅ CH₃ H 4- F F F—(CH₂)₂—O—(CH₂)₂— CH(CH₃)₂ b) I-8-b-4 C₂H₅ CH₃ H 4- F F F —(CH₂)₄—C(CH₃)₃ c) I-8-b-5 CH₃ CH₃ H 4- F F F —(CH₂)₄— CH(CH₃)₂ d) I-8-b-6 CH₃CH₃ H 4- F F F —(CH₂)₂—O—(CH₂)₂— C(CH₃)₃ e) I-8-b-7 CH₃ CH₃ H 4- F F F—(CH₂)₂—O—(CH₂)₂— CH(CH₃)₂ f) a) ¹H NMR (400 MHz, CDCl₃): 6.67 (s, 2H,Ar—H), 4.32 (q, 2H, OCH₂CF₃), 3.86 (m, 4H, CH₂—N), 1.03 (s, 9H, t-Bu) b)¹H NMR (400 MHz, CDCl₃): 6.67 and 6.62 (each d, 1H, Ar—H), 4.32 (q, 2H,OCH₂CF₃), 2.47 (m, 1H, CH(CH₃)₂) c) ¹H NMR (400 MHz, CDCl₃): 6.67 and6.62 (each d, 1H, Ar—H), 4.32 (q, 2H, OCH₂CF₃), 1.92 (m, 4H, CH₂), 1.09(d, 9H, t-Bu) d) ¹H NMR (400 MHz, CDCl₃): 6.62 (s, 2H, Ar—H), 4.32 (q,2H, OCH₂CH₃), 1.92 (m, 4H, CH₂), 1.05 (d, 6H, CH(CH₃)₂) e) ¹H NMR (400MHz, CDCl₃): 6.62 (s, 2H, Ar—H), 4.32 (q, 2H, OCH₂CH₃), 3.88 (m, 4H,CH₂—N), 1.08 (s, 9H, t-Bu) f) ¹H NMR (400 MHz, CDCl₃): 6.64 (s, 2H,Ar—H), 4.32 (q, 2H, OCH₂CH₃), 3.87 (m, 4H, CH₂—N), 1.02 (d, 9H,CH(CH₃)₂)

Example I-8-c-1

0.58 g of inventive compound I-8-a-4 is dissolved in 5 ml ofdichloromethane and admixed with 0.187 g of ethyl chloroformate and0.206 g of triethylamine. The mixture is left to stir at roomtemperature for 18 h, and 10 ml of water are added. After extracting theaqueous phase using an extraction cartridge, the mixture is concentratedand purified by means of preparative HPLC (RP-18, acetonitrile/watergradient (1% trifluoroacetic acid)). This gives 0.03 g of inventivecompound I-8-c-1.

In analogy to example (I-8-c-1), and according to the generalinformation regarding preparation, the following compounds of theformula (I-8-c) are obtained.

(I-8-c)

Ex. No. W X Y Z J¹ J² J³ A D L M R² Analysis I-8-c-1 C₂H₅ CH₃ H 4- F F F—(CH₂)₄— O O C₂H₅ a) I-8-c-2 C₂H₅ CH₃ H 4- F F F —(CH₂)₂—O—(CH₂)₂— O OC₂H₅ b) I-8-c-3 C₂H₅ C₂H₅ H 4- F F F —(CH₂)₂—O—(CH₂)₂— O O C₂H₅ c)I-8-c-4 C₂H₅ C₂H₅ H 4- F F F —(CH₂)₄— O O C₂H₅ d) I-8-c-5 CH₃ CH₃ H 4- FF F —(CH₂)₂—O—(CH₂)₂— O O C₂H₅ e) I-8-c-6 CH₃ CH₃ H 4- F F F —(CH₂)₄— OO C₂H₅ f) a) ¹H NMR (400 MHz CDCl₃): 6.70 (s, 1H, Ar—H), 6.67 (s, 1H,Ar—H), 4.32 (m, 2H, CF₃—CH₂)₂, 4.14 (m, 2H, CH₂—OC(═O)) b) ¹H NMR (400MHz CDCl₃): 6.70 (d, 1H, Ar—H), 6.65 (d, 1H, Ar—H), 4.32 (m, 2H,CF₃—CH₂)₂, 4.16 (m, 2H, CH₂—OC(═O)) c) ¹H NMR (400 MHz CDCl₃): 6.68 (d,2H, Ar—H), 4.32 (m, 2H, CF₃—CH₂), 4.14 (m, 2H, CH₂—OC(═O)) d) ¹H NMR(400 MHz CDCl₃): 6.68 (d, 2H, Ar—H), 4.34 (m, 2H, CF₃—CH₂), 4.16 (m, 2H,CH₂—OC(═O)) e) ¹H NMR (400 MHz CDCl₃): 6.68 (d, 2H, Ar—H), 4.30 (m, 2H,CF₃—CH₂), 4.17 (m, 2H, CH₂—OC(═O)) f) ¹H NMR (400 MHz CDCl₃): 6.65 (d,2H, Ar—H), 4.32 (m, 2H, CF₃—CH₂), 4.16 (m, 2H, CH₂—OC(═O))

2,6-Dimethyl-4-trifluoroethoxyphenylacetic acid (Example XXXI-1)

18.05 g (451 mmol) of sodium hydride are initially charged in 500 ml ofDMF, 41.05 g (410 mmol) of trifluoroethanol are added dropwise, afterthe evolution of gas has ended 15.63 g (82 mmol) of copper(I) iodide areadded, a solution of 21.10 g (82 mmol) of methyl2,6-dimethyl-4-bromophenylacetate in 100 ml of DMF is slowly addeddropwise and the mixture is boiled at reflux for 2.5 h.

For workup, the mixture is concentrated, the residue is admixed withwater and extracted by shaking repeatedly with diethyl ether, and theether phase is dried, filtered and concentrated:

12.73 g of N,N-dimethyl-4-trifluoroethoxyphenylacetamide.

The aqueous phase is acidified with hydrochloric acid and extractedrepeatedly with dichloromethane, and the organic phase is dried andconcentrated by rotary evaporation:

7.66 g or arylacetic acid.

The 12.73 g ofN,N-dimethyl-2,6-dimethyl-4-trifluoroethoxyphenylacetamide are boiled ina solution of 58 g of potassium hydroxide in 165 ml of methanol and 43ml of water for 36 h. For workup, the methanol is removed by rotaryevaporation, the residue is partitioned between water anddichloromethane, the aqueous phase is acidified with hydrochloric acidand the precipitated crystals are filtered off with suction and dried.In this way, a further 11.6 g of the phenylacetic acid (XXXI-1) areobtained.

Total yield: 19.3 g (90% of theory) of2,6-dimethyl-4-trifluoroethoxyphenylacetic acid (XXXI-1).

1H NMR (d₆-DMSO): δ=2.25 (s, 6H), 3.50 (s, 2H), 4.60 (m, 2H), 6.75 (s,2H) ppm.

logP (HCOOH) 2.51.

The logP values reported in the above tables and preparation examplesare determined according to EEC Directive 79/831 Annex V.A8 by HPLC(High Performance Liquid Chromatography) on a reversed-phase column(C18). Temperature: 43° C.

The determination is effected in the acidic range at pH 2.3 with 0.1%aqueous phosphoric acid and acetonitrile as eluent; linear gradient from10% acetonitrile to 95% acetonitrile.

The determination by LC-MS in the acidic range is effected at pH 2.7with 0.1% aqueous formic acid and acetonitrile (contains 0.1% formicacid) as the eluent; linear gradient from 10% acetonitrile to 95%acetonitrile.

The determination by LC-MS in the neutral range is effected at pH 7.8with 0.001 molar aqueous ammonium hydrogen carbonate solution andacetonitrile as the eluent; linear gradient from 10% acetonitrile to 95%acetonitrile.

The calibration is effected with unbranched alkane-2-ones (with 3 to 16carbon atoms), the logP values of which are known (determination of logPvalues on the basis of the retention times by linear interpolationbetween two successive alkanones).

The lambda-max values were determined using the UV spectra from 200 nmto 400 nm in the maxima of the chromatographic signals.

APPLICATION EXAMPLES Example 1 Myzus Test (MYZUPE Spray Treatment)

Solvent: 78 parts by weight of acetone 1.5 parts by weight ofdimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycolether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Discs of Chinese cabbage (Brassica pekinensis) infected by all stages ofthe green peach aphid (Myzus persicae) are sprayed with an activeingredient preparation of the desired concentration.

After the desired time, the effect in % is determined. 100% means thatall of the aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, for example, the following compounds from the preparationexamples show, at an application rate of 500 g/ha, an effect of ≧80%:

Ex. No.: I-1-a-1, I-1-a-3, I-1-a-4, I-1-a-5, I-1-a-6, I-1-a-7, I-1-a-8,I-1-a-10, I-1-a-12, I-1-a-13, I-1-a-14, I-1-a-15, I-1-a-17, I-1-a-18,I-1-a-19, I-1-a-23, I-1-a-24, I-1-a-25, I-1-a-26, I-1-a-27, I-1-a-28,I-1-a-29, I-1-a-30, I-1-a-31, I-1-a-32, I-1-a-33, I-1-a-34, I-1-a-35,I-1-a-36, I-1-a-37, I-1-a-38, I-1-a-39, I-1-a-40, I-1-a-41, I-1-a-42,I-1-a-43, I-1-a-44, I-1-a-45, I-1-a-46, I-1-a-48, I-1-b-1, I-1-c-1,I-1-c-2, I-1-c-3, I-1-c-4, I-1-c-5, I-1-c-6, I-2-a-1, I-2-a-2, I-2-a-3,I-2-a-4, I-2-a-5, I-2-a-6, I-8-a-2, I-8-b-3, I-8-b-5

In this test, for example, the following compounds from the preparationexamples show, at an application rate of 20 g/ha, an effect of ≧80%:

Ex. No.: I-1-a-20

Example 2 Phaedon Test (PHAECO Spray Treatment)

Solvent: 78.0 parts by weight of acetone 1.5 parts by weight ofdimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycolether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Discs of Chinese cabbage (Brassica pekinensis) are sprayed with anactive ingredient preparation of the desired concentration and, afterdrying, populated with larvae of the mustard beetle (Phaedoncochleariae).

After the desired time, the effect in % is determined. 100% means thatall beetle larvae have been killed; 0% means that none of the beetlelarvae have been killed.

In this test, for example, the following compounds of the preparationexamples show, at an application rate of 500 g/ha, an effect of ≧80%:

Ex. No.: I-1-a-1, I-1-a-3, I-1-a-8, I-1-a-11, I-1-a-13, I-1-a-14,I-1-a-15, I-1-a-16, I-1-a-18, I-1-a-19, I-1-a-21, I-1-a-23, I-1-a-27,I-1-a-28, I-1-a-30, I-1-a-31, I-1-a-32, I-1-a-33, I-1-c-6, I-2-a-5

Example 3 Tetranychus Test; OP-Resistant (TETRUR Spray Treatment)

Solvent: 78.0 parts by weight of acetone 1.5 parts by weight ofdimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycolether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted to the desiredconcentration with emulsifier-containing water.

Discs of french bean leaves (Phaseolus vulgaris) infested with allstages of the two-spotted spider mite (Tetranychus urticae) are sprayedwith a preparation of the active ingredient at the desiredconcentration.

After the desired time, the effect in % is determined. 100% means thatall spider mites have been killed and 0% means that none of the spidermites have been killed.

In this test, for example, the following compounds from the preparationexamples show an effect of ≧80% at an application rate of 100 g/ha.

Ex. No.: I-1-a-4, I-1-a-5, I-1-a-6, I-1-a-7, I-1-a-8, I-1-a-10,I-1-a-14, I-1-a-17, I-1-a-2, I-1-a-25, I-1-a-26, I-1-a-28, I-1-a-3,I-1-a-30, I-1-a-31, I-1-a-32, I-1-b-1, I-1-c-1, I-1-c-2, I-1-c-3,I-1-c-4, I-1-c-5, I-1-c-6, I-2-a-5, I-2-a-6, I-2-b-1, I-8-c-1, I-8-a-2,I-8-b-3, I-8-b-5

In this test, for example, the following compounds from the preparationexamples shown an effect of ≧80% at an application rate of 20 g/ha.

Ex. No.: I-1-a-16, I-1-a-19

Example 4 Spodoptera frugiperda Test (SPODFR Spray Treatment)

Solvent: 78.0 parts by weight of acetone 1.5 parts by weight ofdimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycolether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted withemulsifier-containing water to the desired concentration.

Discs of maize leaves (Zea mays) are sprayed with an active ingredientpreparation of the desired concentration and, after drying, populatedwith caterpillars of the army worm (Spodoptera frugiperda).

After the desired time, the effect in % is determined. 100% means thatall caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, the following compounds from the preparationexamples show, at an application rate of 500 g/ha, an effect of ≧80%:

Ex. No.: I-1-a-27, I-1-a-28, I-1-a-32, I-1-a-36, I-1-a-39, I-1-c-1

Example 5 Meloidogyne incognita Test (MELGIN)

Solvent: 78.0 parts by weight of acetone 1.5 parts by weight ofdimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycolether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted to the desiredconcentration with water.

Vessels are filled with sand, solution of active ingredient, Meloidogyneincognita egg/larvae suspension and lettuce seeds. The lettuce seedsgerminate and the plants develop. On the roots, galls are formed.

After the desired time, the nematicidal effect is determined by the gallformation in %. 100% means that no galls were found; 0% means that thenumber of galls on the treated plants corresponds to that of theuntreated control.

In this test, for example, the following compounds from the preparationexamples show an effect of ≧80% at an application rate of 20 ppm:

Ex. No.: I-1-a-25, I-1-c-6

Example 6 Lucilia cuprina Test (LUCICU)

Solvent: dimethyl sulphoxide

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with water.

Vessels containing horse meat treated with the active ingredientpreparation of the desired concentration are populated with Luciliacuprina larvae.

After the desired time, the kill in % is determined. 100% means that allof the larvae have been killed; 0% means that none of the larvae havebeen killed.

In this test, for example, the following compounds from the preparationexamples show, at an application rate of 100 ppm, an effect of ≧80%:

Ex. No.: I-1-a-25, I-1-a-3, I-2-a-5, I-2-a-6

Example 7 Boophilus microplus Test (BOOPMI Injection)

Solvent: dimethyl sulphoxide

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amount of solvent,and the concentrate is diluted to the desired concentration with water.The solution of active ingredient is injected into the abdomen(Boophilus microplus), and the animals are transferred into dishes andkept in a climate-controlled room. The activity is assessed by laying offertile eggs.

After the desired time, the effect in % is determined, 100% means thatnone of the ticks has laid any fertile eggs

In this test, for example, the following compounds from the preparationexamples show, at an application rate of 20 ppm, an effect of ≧80%:

Ex. No.: I-1-a-25, I-1-a-3, I-1-a-7, I-1-c-4, I-1-c-5, I-2-a-5, I-2-a-6

Example 8 Enhancement of Activity by Ammonium/Phosphonium Salts inCombination with Penetration Enhancers

Myzus persicae Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amount of solventand emulsifier, and the concentrate is diluted to the desiredconcentration with water. For application with ammonium or phsophoniumsalts and penetration enhancer (rapeseed oil methyl ester 500 EW), theseare each added to the spray liquor in a concentration of 1000 ppm.

Bell pepper plants (Capsicum annuum) heavily infested by the green peachaphid (Myzus persicae) are treated by spraying to runoff point with theactive ingredient preparation of the desired concentration. After thedesired time, the kill in % is determined. 100% means that all animalshave been killed; 0% means that none of the animals have been killed.

TABLE Kill rate/% after 6 days +AS +RME +RME +AS Active Concen- (1000(1000 (1000 ingredient tration/ppm ppm) ppm) ppm each) I-1-a-25 0.8 0 040 55

Example 9 Aphis gossypsi Test

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part byweight of alkylaryl polyglycol ether

To prepare an appropriate active ingredient preparation, 1 part byweight of active ingredient is mixed with the stated amounts of solventand emulsifier, and the concentrate is diluted to the desiredconcentration with emulsifier-containing water. For application withammonium or phosphonium salts and penetration enhancers (rapeseed oilmethyl ester 500 EW), these are each added to the spray liquor in aconcentration of 1000 ppm.

Cotton plants (Gossypium hirsutum) heavily infested by the cotton aphid(Aphis gossypii) are treated by spraying to runoff point with the activeingredient preparation of the desired concentration.

After the desired time, the kill in % is determined. 100% means that allthe aphids have been killed; 0% means that none of the aphids have beenkilled.

TABLE Kill rate/% after 6 days +AS +RME +RME +AS Active Concen- (1000(1000 (1000 ingredient tration/ppm ppm) ppm) ppm each) I-1-a-25 0.8 0 3520 85 I-1-a-29 4 10 15 80 95 I-1-a-31 4 0 10 5 35

Example 10

-   1. Herbicidal Pre-Emergence Action

Seeds of monocotyledonous and dicotyledonous weed and crop plants areplaced in sandy lam in wood fibre pots and covered with soil. The testcompounds, formulated in the form of wettable powders (WP), are thenapplied to the surface of the covering soil as an aqueous suspensionwith a water application rate of 600 l/ha (converted), with 0.2% addedwetting agent in different dosages.

After the treatment, the pots are placed in a greenhouse and kept undergood growth conditions for the test plants. The visual assessment of theemergence damage on the test plants is effected after a test period ofapprox. three weeks by comparison with the untreated controls(herbicidal effect in per cent: 100% effect=the plants have died, 0%effect=like control plants).

In addition to the aforementioned compounds, the following compounds,applied by the pre-emergence method at 320 g/ha a.i., show an effect of≧80% against Alopecurus myosuroides, Echinocloa crus-galli, Loliummultiflorum and Setaria viridis; I-1-a-6, I-1-a-7, I-1-a-9, I-1-a-12,I-1-a-13, I-1-a-14, I-1-a-16, I-1-a-19, I-1-a-22, I-1-a-33, I-1-a-34,I-1-a-35, I-1-a-37, I-1-a-38, I-1-a-39, I-1-a-40, I-1-a-41, I-1-b-2,I-1-c-2, I-1-c-3, I-1-c-6, I-2-a-5.

In addition to the aforementioned compounds, the following compounds,applied by the pre-emergence method at 80 g/ha a.i., show an effect of≧80% against Alopecurus myosuroides, Echinocloa crus-galli, Loliummultiflorum and Setaria viridis: I-1-a-1, I-1-a-2, I-1-a-3, I-1-a-4,I-1-a-5, I-1-a-8, I-1-a-17, I-1-a-18, I-1-a-21, I-1-a-25, I-1-b-1,I-1-c-1, I-1-c-4, I-1-c-5.

-   2. Herbicidal Post-Emergence Action

Seeds of monocotyledonous and dicotyledonous weed and crop plants areplaced in sandy loam in wood fibre pots, covered with soil andcultivated in a greenhouse under good growth conditions. Two to threeweeks after sowing, the test plants are treated at the one-leaf stage.The test compounds, formulated as wettable powders (WP), are sprayedonto the green parts of the plants in different dosages with a waterapplication rate of 600 l/ha (converted), with 0.2% added wetting agent.After the test plants have been kept in the greenhouse under optimalgrowth conditions for about three weeks, the effect of the preparationsis assessed visually by comparison to untreated controls (herbicidaleffect in per cent: 100% effect=the plants have died, 0% effect=likecontrol plants).

In addition to the aforementioned compounds, the following compounds,applied by the post-emergence method at 80 g/ha, show an effect of ≧80%against Alopecurus myosuroides, Avena fatua, Echinocloa crus-galli,Lolium multiflorum, Setaria viridis and Veronica persica: I-1-a-4,I-1-a-5, I-1-a-6, I-1-a-8, I-1-a-17, I-1-a-18, I-1-a-19, I-1-a-25,I-1-a-26, I-1-a-34, I-1-a-39, I-1-b-1, I-1-b-2, I-1-c-4, I-1-c-5,I-2-a-5.

In addition to the aforementioned compounds, the following compounds,applied by the post-emergence method at 80 g/ha, show an effect of ≧80%against Alopecurus myosuroides, Avena fatua, Echinocloa crus-galli,Lolium multiflorum and Setaria viridis; I-1-a-1, I-1-a-3, I-1-a-7,I-1-a-9, I-1-a-14, I-1-a-35, I-1-a-37, I-1-a-38, I-1-a-40, I-1-a-41,I-1-c-1, I-8-a-1, I-8-c-1, I-8-c-3, I-8-c-5.

Use of Safeners:

If there is to be an additional test as to whether safeners can improvethe plant compatibility of test substances in the case of crop plants,the following options are used for applying the safeners:

-   -   Seeds of the crop plants are, before sowing, dressed with        safener substance (the amount of safener stated in per cent,        based on the weight of the seed)    -   Before the application of the test substances, the crop plants        are sprayed with the safener at a certain application rate per        hectare (usually one day before the application of the test        substances)    -   The safener is applied together with the test substance as a        tankmix (the amount of safener is stated in g/ha or as a ratio,        based on the herbicide).

Container Trials with Cereals in a Greenhouse Mefenpyr 1 day BeforeHerbicide Application

28 days after 28 days after application application Application rateSummer barley Summer wheat g a.i./ha observed (%) observed (%) Ex.(I-1-a-5) 25 95 12.5 65 65 Ex. (I-1-a-5) + 25 + 50 75 mefenpyr 12.5 +50   35 25 28 days after application Application rate Summer wheat ga.i./ha observed (%) Ex. (I-1-a-6) 25 85 12.5 70 Ex. (I-1-a-6) + 25 + 5060 mefenpyr 12.5 + 50   50 Ex. (I-1-a-7) 100 70 50 70 25 50 12.5 50 Ex.(I-1-a-7) + 100 + 50  30 mefenpyr 50 + 50 20 25 + 50 20 12.5 + 50   1010 days after 28 days after application application Application rateSummer wheat Summer wheat g a.i./ha observed (%) observed (%) Ex.(I-1-a-8) 12.5 65 98 Ex. (I-1-a-8) + 12.5 + 50 50 50 mefenpyr 28 daysafter application Application rate Summer wheat g a.i./ha observed (%)Ex. (I-1-a-14) 50 100 25 99 12.5 93 Ex. (I-1-a-14) + 50 + 50 85 mefenpyr25 + 50 85 12.5 + 50   40 28 days after 28 days after applicationapplication Application rate Summer barley Summer wheat g a.i./haobserved (%) observed (%) Ex. (I-1-a-15) 100 60 50 97 40 25 85 30 12.570 10 Ex. (I-1-a-15) + 100 + 50  20 mefenpyr 50 + 50 80 10 25 + 50 80 512.5 + 50   20 0 28 days after application Application rate Summerbarley g a.i./ha observed (%) Ex. (I-1-a-17) 200 95 100 80 50 40 Ex.(I-1-a-17) + 200 + 50 60 mefenpyr 100 + 50 60  50 + 50 30 28 days after28 days after application application Application rate Summer barleySummer wheat g a.i./ha observed (%) observed (%) Ex. (I-1-a-19) 100 8550 70 25 70 20 12.5 10 Ex. (I-1-a-19) + 100 + 50  70 mefenpyr 50 + 50 5025 + 50 40 20 12.5 + 50   0 10 days after 28 days after applicationapplication Application rate Summer wheat Summer wheat g a.i./haobserved (%) observed (%) Ex. (I-1-a-25) 12.5 40 70 Ex. (I-1-a-25) +12.5 + 50 25 30 mefenpyr 10 days after application Application rateSummer barley g a.i./ha observed (%) Ex. (I-1-b-2) 12.5 50 Ex.(I-1-b-2) + 12.5 + 50 20 mefenpyr 28 days after application Applicationrate Summer wheat g a.i./ha observed (%) Ex. (I-1-a-37) 12.5 70 Ex.(I-1-a-37) + 12.5 + 50 15 mefenpyr

Container Tests with Maize-Soya-Cotton in a Greenhouse Cyprosulfamide 1day Before Herbicide Application

28 days after application Application rate Maize (Aventura) g a.i./haobserved (%) Ex. (I-1-a-8) 50 70 25 60 12.5 35 Ex. (I-1-a-8) + 50 + 20040 cyprosulfamide 25 + 200 35 12.5 + 200   15 28 days after 28 daysafter application application Application rate Maize (Arsenal) Maize(Cecilia) g a.i./ha observed (%) observed (%) Ex. (I-1-a-25) 100 100 3550 75 20 25 15 10 12.5 5 0 Ex. (I-1-a-25) + 100 + 100  70 10cyprosulfamide 50 + 100 50 0 25 + 100 0 0 12.5 + 100   0 0 Ex. (I-1-c-2)100 25 75 50 20 25 20 Ex. (I-1-c-2) + 100 + 200  15 25 cyprosulfamide50 + 200 0 25 + 200 0

1-21. (canceled)
 22. A compound of formula (II)

in which W is hydrogen, alkyl, halogen, haloalkyl, alkoxy or haloalkoxy,X is alkyl, alkenyl, alkynyl, halogen, alkoxy, haloalkyl, haloalkoxy orcyano, Y is hydrogen, alkyl, alkoxy or halogen, Z is a group

in which J¹ and J² are each independently hydrogen or halogen and J³ ishalogen or a haloalkyl group, A is hydrogen, in each case optionallyhalogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, or issaturated or unsaturated, optionally substituted cycloalkyl in which atleast one ring atom is optionally replaced by a heteroatom, or in eachcase optionally halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-,cyano- or nitro-substituted aryl, arylalkyl or hetaryl, B is hydrogen,alkyl or alkoxyalkyl, or A and B together with the carbon atom to whichthey are bonded are a saturated or unsaturated, unsubstituted orsubstituted cycle optionally containing at least one heteroatom, D ishydrogen or an optionally substituted radical from the group of alkyl,alkenyl, alkynyl, alkoxyalkyl, saturated or unsaturated cycloalkyl inwhich one or more ring members are optionally replaced by heteroatoms,or in each case optionally substituted arylalkyl, aryl, hetarylalkyl orhetaryl, or A and D together with the atoms to which they are bonded area saturated or unsaturated cycle which is unsubstituted or substitutedin the A, D moiety and optionally contains at least one heteroatom, andR⁸ is alkyl. 23-25. (canceled)
 26. A compound of formula (XXXI)

in which W is hydrogen, alkyl, halogen, haloalkyl, alkoxy or haloalkoxy,X is alkyl, alkenyl, alkynyl, halogen, alkoxy, haloalkyl, haloalkoxy orcyano, Y is hydrogen, alkyl, alkoxy or halogen, and Z is a group

in which J¹ and J² are each independently hydrogen or halogen and J³ ishalogen or a haloalkyl group. 27-33. (canceled)
 34. The compoundaccording to claim 22, in which W is hydrogen, C₁-C₆-alkyl, halogen,C₁-C₆-alkoxy, C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy, X is halogen,C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy,C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or cyano, Y is hydrogen, halogen,C₁-C₆-alkyl or C₁-C₆-alkoxy, Z is a group

in which J¹ and J² are each independently hydrogen, fluorine orchlorine, and J³ is halogen or C₁-C₄-haloalkyl, A is hydrogen or in eachcase optionally halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl,C₁-C₁₀-alkoxy-C₁-C₈-alkyl, C₁-C₁₀-alkylthio-C₁-C₆-alkyl, optionallyhalogen-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl inwhich one or two ring members not directly adjacent are optionallyreplaced by oxygen and/or sulphur, or is in each case optionallyhalogen-C₁-C₆-alkyl-, C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-,C₁-C₆-haloalkoxy-, cyano- or nitro-substituted phenyl, naphthyl, hetarylhaving 5 to 6 ring atoms, phenyl-C₁-C₆-alkyl or naphthyl-C₁-C₆-alkyl, Bis hydrogen, C₁-C₁₂-alkyl or C₁-C₈-alkoxy-C₁-C₆-alkyl, or A, B and thecarbon atom to which they are bonded are saturated C₃-C₁₀-cycloalkyl orunsaturated C₅-C₁₀-cycloalkyl, in which one ring member is optionallyreplaced by nitrogen, oxygen or sulphur and which is optionally mono- ordisubstituted by C₁-C₈-alkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyloxy,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkoxy,C₃-C₁₀-cycloalkyl, C₁-C₈-haloalkyl, C₂-C₆-haloalkoxy,C₁-C₆-alkoxy-C₁-C₄-alkoxy, where the aforementioned radicals are alsopossible nitrogen substituents, or A, B and the carbon atom to whichthey are bonded are C₃-C₆-cycloalkyl which is substituted by anoptionally C₁-C₄-alkyl-substituted alkylenediyl group optionallycontaining one or or two oxygen and/or sulphur atoms which are notdirectly adjacent, or by an alkylenedioxyl or by an alkylenedithioylgroup, which group forms a further five- to eight-membered ring with thecarbon atom to which it is bonded, or A, B and the carbon atom to whichthey are bonded are C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, in which twosubstituents together with the carbon atoms to which they are bonded arein each case optionally C₁-C₆-alkyl-, C₁-C₆-alkoxy- orhalogen-substituted C₂-C₆-alkanediyl, C₂-C₆-alkenediyl orC₄-C₆-alkadienediyl in which one methylene group is optionally replacedby oxygen or sulphur, D is hydrogen, in each case optionallyhalogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl,C₁-C₁₀-alkoxy-C₁-C₈-alkyl, optionally halogen-, C₁-C₄-alkyl-,C₁-C₄-alkoxy- or C₁-C₄-haloalkyl-substituted C₃-C₈-cycloalkyl, in whichone ring member is optionally replaced by oxygen or sulphur, or in eachcase optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-,C₁-C₆-haloalkoxy-, cyano- or nitro-substituted phenyl, hetaryl having 5or 6 ring atoms, phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl having 5 or 6ring atoms, or A and D together are in each case optionally substitutedC₃-C₆-alkanediyl or C₃-C₆-alkenediyl, in which one methylene group isoptionally replaced by a carbonyl group, oxygen or sulphur, and wherepossible substituents in each case are: halogen, hydroxyl, mercapto orin each case optionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy,C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy, or a furtherC₃-C₆-alkanediyl moiety, C₃-C₆-alkenediyl moiety or a butadienyl moiety,which is optionally substituted by C₁-C₆-alkyl or in which two adjacentsubstituents with the carbon atoms to which they are bonded optionallyform a further saturated or unsaturated cycle having 5 or 6 ring atoms.35. The compound according to claim 22, in which W is hydrogen,fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkylor C₁-C₂-haloalkoxy, X is chlorine, bromine, iodine, C₁-C₄-alkyl,C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl,C₁-C₂-haloalkoxy or cyano, Y is hydrogen, methyl, ethyl, fluorine,chlorine, bromine, iodine, methoxy or ethoxy, Z is the group

in which J¹ and J² are each independently hydrogen, fluorine orchlorine, and J³ is fluorine, chlorine, trichloromethyl, difluoromethyl,difluorochloromethyl, dichlorofluoromethyl or trifluoromethyl, A ishydrogen, in each case optionally mono- to tri-fluorine- or-chlorine-substituted C₁-C₆-alkyl, C₁-C₄-alkoxy-C₁-C₂-alkyl, optionallymono- to di-C₁-C₂-alkyl- or -C₁-C₂-alkoxy-substituted C₃-C₆-cycloalkyloptionally interrupted by one oxygen atom, B is hydrogen, C₁-C₄-alkyl orC₁-C₂-alkoxy-C₁-C₂-alkyl, or A, B and the carbon atom to which they arebonded are saturated or unsaturated C₃-C₇-cycloalkyl in which one ringmember is optionally replaced by nitrogen, oxygen or sulphur and whichis optionally mono- to di-C₁-C₆-alkyl-, -C₁-C₄-alkoxy-C₁-C₂-alkyl-,-trifluoromethyl-, -C₁-C₆-alkoxy-, -C₃-C₆-alkenyloxy-,-trifluoroethoxy-, -C₁-C₃-alkoxy-C₁-C₃-alkoxy- or-C₃-C₆-cycloalkylmethoxy-substituted, where the aforementioned radicalsare also possible nitrogen substituents, or A, B and the carbon atom towhich they are bonded are C₅-C₆-cycloalkyl which is substituted by anoptionally methyl- or ethyl-substituted alkylenediyl group optionallycontaining one or two oxygen or sulphur atoms not directly adjacent orby an alkylenedioxy group or by an alkylenedithiol group, which groupforms, with the carbon atom to which it is bonded, a further five- orsix-membered ring, or A, B and the carbon atom to which they are bondedare C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which two substituentstogether with the carbon atoms to which they are bonded are in each caseoptionally C₁-C₂-alkyl- or C₁-C₂-alkoxy-substituted C₂-C₄-alkanediyl,C₂-C₄-alkenediyl or butadienediyl, D is hydrogen, in each caseoptionally mono- to tri-fluorine-substituted C₁-C₆-alkyl, C₃-C₆-alkenyl,C₁-C₄-alkoxy-C₁-C₃-alkyl, in each case optionally mono- todi-C₁-C₄-alkyl-, -C₁-C₄-alkoxy- or -C₁-C₂-haloalkyl-substitutedC₃-C₆-cycloalkyl in which one methylene group is optionally replaced byoxygen, or A and D together are optionally mono- to disubstitutedC₃-C₅-alkanediyl in which one methylene group may be replaced by acarbonyl group, oxygen or sulphur, where the substituents areC₁-C₂-alkyl or C₁-C₂-alkoxy, or or A and D together are C₃-C₅-alkanediylwhich is optionally substituted by an optionally mono- totetra-C₁-C₄-alkyl- or -C₁-C₃-alkoxy-C₁-C₂-alkyl-substitutedalkylenedioxy group containing two oxygen atoms not directly adjacent,to form a further 5- or 6-membered ring.
 36. The compound according toclaim 22, in which W is hydrogen, chlorine, methyl or ethyl, X ischlorine, methyl, ethyl, methoxy or ethoxy, Y is hydrogen, methyl orchlorine, Z is the group

in which J¹ and J² are each independently hydrogen or fluorine and J³ isfluorine, chlorine or trifluoromethyl, A is hydrogen, in each caseoptionally mono- to tri-fluorine-substituted C₁-C₄-alkyl orC₁-C₂-alkoxy-C₁-C₂-alkyl, or is cyclopropyl, cyclopentyl or cyclohexyl,B is hydrogen, methyl or ethyl, or A, B and the carbon atom to whichthey are bonded are saturated C₅-C₆-cycloalkyl in which one ring memberis optionally replaced by nitrogen, oxygen or sulphur and which isoptionally mono- or di-methyl-, -ethyl-, -methoxymethyl-,-ethoxymethyl-, -methoxyethyl-, -ethoxyethyl-, -trifluoromethyl-,-methoxy-, -ethoxy-, -propoxy-, -butoxy-, -methoxyethoxy-,-ethoxyethoxy-, -allyloxy-, -trifluoroethoxy- or-cyclopropylmethoxy-substituted, where the aforementioned radicals arealso possible nitrogen substitutents, or A, B and the carbon atom towhich they are bonded are C₆-cycloalkyl which is optionally substitutedby an alkylidenediyl group optionally interrupted by one oxygen atom orby an alkylenedioxy group optionally containing two oxygen atoms notdirectly adjacent, to form a further 5- or 6-membered ring which isoptionally mono- or di-methyl-substituted, or A, B and the carbon atomto which they are bonded are C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl, inwhich two substituents together with the carbon atoms to which they arebonded are C₂-C₄-alkanediyl or C₂-C₄-alkenediyl or butadienediyl, D ishydrogen, in each case optionally mono- to tri-fluorine-substitutedC₁-C₄-alkyl, C₃-C₄-alkenyl, C₁-C₄-alkoxy-C₁-C₃-alkyl, or is cyclopropyl,cyclopentyl or cyclohexyl, or (in the case of the compounds of theformula (I-4)) is in each case optionally mono-fluorine-, -chlorine-,-methyl-, -ethyl-, -n-propyl-, -isopropyl-, -methoxy-, -ethoxy- or-trifluoromethyl-substituted phenyl or pyridyl, or A and D together areoptionally mono-methyl- or -methoxy-substituted C₃-C₅-alkanediyl inwhich one carbon atom is optionally replaced by a carbonyl group, or Aand D together are C₃-C₅-alkanediyl which is optionally substituted byan optionally mono- to di-C₁-C₂-alkyl-substituted alkylenedioxy groupcontaining two oxygen atoms not directly adjacent, to form a further5-membered ring.
 37. The compound according to claim 22, In which W ishydrogen, methyl or ethyl, X is chlorine, methyl or ethyl, Y ishydrogen, Z is OCH₂—CF₃ in the 3 position, OCH₂—CF₃ in the 4 position,or OCH₂—CF₃ in the 5 position. A is methyl or ethyl, B is hydrogen ormethyl, A, B and the carbon atom to which they are bonded are saturatedC₅-C₆-cycloalkyl in which one ring member is optionally replaced byoxygen and which is optionally mono- or di-methyl-, -ethyl-,-methoxymethyl-, -methoxy-, -ethoxy-, -propoxy-, -butoxy-,-trifluoroethoxy-substituted, or A, B and the carbon atom to which theyare bonded are C₆-cycloalkyl which is optionally substituted by analkylenedioxy group containing two oxygen atoms not directly adjacent,to form a further 5- or 6-membered ring which is optionally mono- ordi-methyl-substituted, D is hydrogen, or A and D together areC₃-C₅-alkanediyl in which one carbon atom is optionally replaced byoxygen, or A and D together are C₃-C₅-alkanediyl which is optionallysubstituted by an optionally mono- to di-methyl-substitutedalkylenedioxy group optionally containing two oxygen atoms not directlyadjacent, to form a further 5-membered ring.
 38. The compound accordingto claim 26, in which W is hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy,C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy, X is halogen, C₁-C₆-alkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl,C₁-C₄-haloalkoxy or cyano, Y is hydrogen, halogen, C₁-C₆-alkyl orC₁-C₆-alkoxy, and Z is a group

in which J¹ and J² are each independently hydrogen, fluorine orchlorine, and J³ is halogen or C₁-C₄-haloalkyl.
 39. The compoundaccording to claim 26, in which W is hydrogen, fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy,X is chlorine, bromine, iodine, C₁-C₄-alkyl, C₂-C₄-alkenyl,C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy or cyano,Y is hydrogen, methyl, ethyl, fluorine, chlorine, bromine, iodine,methoxy or ethoxy, and Z is the group

in which J¹ and J² are each independently hydrogen, fluorine orchlorine, and J³ is fluorine, chlorine, trichloromethyl, difluoromethyl,difluorochloromethyl, dichlorofluoromethyl or trifluoromethyl.
 40. Thecompound according to claim 26, in which W is hydrogen, chlorine, methylor ethyl, X is chlorine, methyl, ethyl, methoxy or ethoxy, Y ishydrogen, methyl or chlorine, and Z is the group

in which J¹ and J² are each independently hydrogen or fluorine and J³ isfluorine, chlorine or trifluoromethyl.
 41. The compound of claim 26, inwhich W is hydrogen, methyl or ethyl, X is chlorine, methyl or ethyl, Yis hydrogen, and Z is OCH₂—CF₃ in the 3 position, OCH₂—CF₃ in the 4position, or OCH₂—CF₃ in the 5 position.